CN109641366A

CN109641366A - Subparticle composition

Info

Publication number: CN109641366A
Application number: CN201780038033.7A
Authority: CN
Inventors: N·P·梅纳德
Original assignee: Press Technology Co Ltd
Current assignee: Press Technology Co Ltd
Priority date: 2016-06-10
Filing date: 2017-05-29
Publication date: 2019-04-16
Also published as: EP3468755A1; KR20190038534A; US20190255730A1; CA3025903A1; CL2018003542A1; AU2017278043A1; WO2017212368A1; JP2019520302A; EP3468755A4

Abstract

Disclose a kind of method for preparing the composition comprising metal salt subparticle.The method includes to provide to wrap metalliferous alkaline aqueous solution, one or more ligands that can form soluble complexes with metal under alkaline condition and optional one or more dispersing agents；And mix solution to reduce the pH of solution with carbon dioxide source, so as to metal salt subparticle precipitating.Also disclose the composition prepared by the method.A kind of method for handling the matrix as timber is also disclosed, it includes the matrixes for applying the composition and handling by the method.

Description

Subparticle composition

Technical field

The present invention relates to a kind of methods for preparing the composition comprising metal salt subparticle, and are related to passing through the method The composition of preparation.The invention further relates to a kind of methods for handling matrix, and it includes application compositions, and are related to through the side The matrix of method processing.

Background technique

The method of composition of the preparation comprising subparticle may include right presence or absence of water or solvent Or mixtures thereof compound is ground.In wood preservation industry, metallic compound is wet milled as submicron-scale in recent years； These compounds generally comprise copper carbonate or Kocide SD.

The composition being thusly-formed can be used to handle the matrix as timber.Processing method can be according to application composition Whether the property and infiltration matrix surface of matrix need composition and change.Many known methods include that biocide is very molten Liquid, biocide suspension or fine suspension, encapsulated biocide and biocide lotion or microemulsion are as example.

Such as ligno-cellulosic materials would generally be handled after cutting down and grinding trees with biocide, to prolong Its long service life.Plant living is usually just handled in growth, to make for good health and promote the good production of crop Rate.Leather (animal hide) is handled after processing fresh meat.All these organic matrixs all can be by degradation biological body (example Such as bacterium, fungi and insect) attack.In the presence of the other matrixes for the attack that may be subjected to this organism, such as spraying The surface of object and concrete.This attack can reduce the service life of these matrixes, make appearance degradation, and can be due to failure And generate alternative cost or potential hazard.Degradation may reduce crop yield in plant etc..

Pass through various physics using the product of different characteristics to slow down to be developed by these pest infections or infection The method that process handles these matrixes with various chemicals.

Lignocellulosic matrix includes complex structure comprising the wood cell interconnected by pit, the pit packet Film is included, valve system is in addition acted also as when Qi Dangshu is living.When attempting to handle the inside of the matrix, this cell and cell connect Connecing can hinder preservative to flow into matrix.It is especially true when matrix is dry, this is because pit membrane can aspirate, that is, Say that they can collapse into the either side of pit and effectively close it.But due to needing space preservative, with Preservative is dried matrix before being handled critically important.

Certain modern preservatives of timber include ammoniacal copper quaternary (Ammoniacal Copper Quaternary) and copper azoles (Copper Azole) etc..They require addition ammonia or amine to dissolve copper component, and they must be protected in use It stays in the composition.Ammonia is a kind of toxic gas, can also be caused damages to staff other than increasing cost.Make Ammonia is substituted with amine, but they can be such that cost deteriorates.

A kind of important component of ammoniacal copper quaternary composition is copper carbonate, also referred to as basic copper carbonate.Conventional production method packet Acid copper sulfate solution is included to react with sodium carbonate.All compositions of copper carbonate containing ammonia are all true solutions, can be promoted into matrix Dipping, but be therefore corrosive by there is dissolved cation copper substance, and be easy from processed matrix It leaches.

Many conventional solubles as chromated copper arenate (Copper Chrome Arsenate) and ammoniacal copper quaternary are killed livestock One problem of agent is corrosiveness.In the Res fungibiles for attempting not will receive disadvantage influence in industry.

Preservative or biocidal composition can also be used in matrix living, including be used to handle plant.It must not wrap carefully Include phytotoxic component.Such as it must be without too high amount for being applied to the insecticide of plant living or fungicide Organic solvent, such as dimethylbenzene, this is because this may result in Plant death.In addition, fungicide must be about as neutrality Otherwise pH may cause damages to plant.Most of cupric plant protection product is all based on insoluble compound, and main cause is Soluble copper compound is toxic to plant, and is easy to be washed into environment.Routine for plant it is insoluble it is copper-based kill it is true The example of microbial inoculum includes the Bordeaux mixture comprising Kocide SD, and the mixing of the Burgundy comprising basic copper carbonate Object.

This compound may further be used to handle abiotic matrix, such as leather, concrete etc..

Similarly, metallic compound can be used as pigment and catalyst in many industrial circles.

Performance can be significantly increased when metallic compound is made of low particle size.This includes biocide, pigment and urges Agent.A trend present in the present age is using smaller and smaller particle size, including nano particle.Due to higher biology Availability and/or higher pigmentation and/or higher catalytic value, these metallic compounds preferably have the particle ruler of very little Very little and big surface area, to enhance its biological nature, visual characteristic or catalysis characteristics.

The present age biocidal composition include may be inflammable, toxic, environmentally harmful component.Selected biocidal Any component except agent all can increase cost for composition.

Colloidal state water preservative was in the public eye close to 100 years.For example, GB387819 introduction uses colloidal state trisulfides two Ascu saves timber.

In order to handle timber etc., particle size should be less than 1 micron, otherwise may block up into the passage aisle of matrix Plug, it is poor so as to cause the infiltration and distribution of preservative.

One of the performance of the sub-micron biocide prepared by wet grinding may be will affect when for wood preservation Problem is wood matrix with the neutral pH between 4 and 5.By wet grinding prepare sub-micron biocide usually have 7 with PH between 10, therefore since the buffer function of matrix may become unstable when being used to and handling acid higher timber, Especially when using vacuum/pressurized repetitive cycling technology in treatment process.Antiseptic composition frequently makes in many circulations With, therefore the particle kinetics in the composition may change, this may will affect particle size.If particle size increases If adding, because there is the possibility penetrated into and be deteriorated in the blocking in channel.

Similarly, for containing sub-micron pigment (especially inorganic pigment, such as green copper carbonate, white zinc carbonate, shallow Green nickelous carbonate, cupric oxide, green copper borate) composition there are markets.All these compounds are used equally for ceramics And it is used as catalyst.It may include this pigment in timber preservative to enhance the color of processing timber.It is also expensive for producing them 's.

Transition metal oxide is used as catalyst.Example includes that cupric oxide nano particle is used in the catalysis oxidation of methanol With nickel oxide nano particle.It include zinc oxide and copper oxide for converting the catalyst of carbon monoxide and hydrogen.

Persistently there is demand in the method for the composition to preparation comprising metal salt subparticle.

The purpose of the present invention is meet this needs, and/or at least useful choosing of public's offer to a certain extent It selects.

Other purposes of the invention may become apparent from by being described below for providing by way of example.

Any discussion of the file, movement, material, device, the product that include in this specification etc. only merely for be the present invention The purpose of background is provided.Should not be construed as recognizing any or all these content formed prior art basis a part or It is well known general knowledge in field related to the present invention, exists before priority date just as it the same.

Summary of the invention

In one aspect, the present invention provides a kind of method for preparing the composition comprising metal salt subparticle, the side Method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and optional one or more dispersing agents；

Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide Water-based composition comprising metal salt subparticle.

On the other hand, the present invention provides a kind of method for preparing the composition comprising metal salt subparticle, described Method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and one or more dispersing agents；

Following embodiment and can preferably relate separately to or with wherein two or more any any combination be related to Upper aspect and other aspects herein.

In various embodiments, the water-based composition comprising subparticle is colloidal dispersion；Or include subparticle Water-based composition be flocculated composition, and the method further include by the composition go flocculation to provide colloidal state Dispersion.

In various embodiments, the water-based composition comprising subparticle is colloidal dispersion.

In various embodiments, the water-based composition comprising subparticle is flocculated composition；And the method into One step includes to go flocculation to provide colloidal dispersion flocculated composition.

In various embodiments, go flocculation comprising diluting the composition flocculated composition.

In other embodiments, go flocculation comprising being ultrasonically treated to the composition flocculated composition.

In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal carbonate Asia Microparticle precipitating.

In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal borate Asia Microparticle precipitating.In some embodiments, metal carbonate subparticle and metal borate subparticle precipitating and/or The subparticle of metal carbonate and metal borate precipitating.

In various embodiments, soluble metal complex compound is decomposed when reducing the pH of alkaline solution.

In various embodiments, the carbon dioxide reaction that soluble metal complex compound can be provided with carbon dioxide source.

In various embodiments, one or more ligands of soluble metal complex compound are discharged from soluble metal complex compound, and And/or the salt of one or more ligands of person's soluble metal complex compound is generated by the decomposition of soluble metal complex compound.

In various embodiments, one or more ligands for being discharged or its generated salt can reduce or prevent Asia The aggregation and/or sedimentation of microparticle.

In certain embodiments, one or more ligands for being discharged or its generated salt are selected from ammonium carbonate, amine Carbonate and glycol.

In various embodiments, the solution further includes the source of one or more acid.In various embodiments, institute State the source that solution further includes one or more weak acid.

In various embodiments, the method includes and mixes solution, carbon dioxide source and one or more weak acid (inciting somebody to action Solution mixed with carbon dioxide source before, in the process and/or later) to reduce the pH of solution, so that metal salt subparticle is heavy It forms sediment.

In various embodiments, the weak acid is the pKa at least about 6,6.5,7,7.5,8,8.5,9,9.5 or 10 Weak acid.In various embodiments, pKa be about 6 to 15,6 to 14,6 to 13,6 to 12,6 to 11,6 to 10,6 to 9.5 or 6 to 9。

In various embodiments, the weak acid be in the water of pH7 can with metal be formed essentially insoluble property salt it is weak Acid.In various embodiments, the weak acid is the salt that can also form essentially insoluble property with metal in the water that pH is about 8 to 9 Weak acid.

In various embodiments, the weak acid is boric acid or phenol.

In various embodiments, the weak acid is boric acid.

In various embodiments, the weak acid is boric acid, and the metal salt precipitated includes metal borate.

In various embodiments, the method includes by source of boric acid (such as boric acid or borate) and to include metal carbonate The composition of subparticle mixes, to provide the composition for including metal borate subparticle.

In various embodiments, weak acid source is boric acid or borate.

In various embodiments, weak acid source is borax.

In various embodiments, the metal salt precipitated includes the salt of weak acid.

In various embodiments, the water-based composition includes metal carbonate subparticle, and the method is into one Step will be comprising that will include that the water-based composition of metal carbonate subparticle is handled with alkali (such as alkali metal hydroxide), to provide Water-based composition comprising metal hydroxides subparticle.In various embodiments, the alkali is alkali or alkaline earth metal Hydroxide.

In various embodiments, the water-based composition includes the subparticle of metal carbonate or metal hydroxides, The method is further included by the water-based composition comprising metal carbonate subparticle or comprising metal hydroxides Asia The water-based composition of microparticle heats, to provide the water-based composition for including metal oxide subparticle.

In various embodiments, the source of carbon dioxide is carbon dioxide gas, wraps carbonated solution, is potential Carbon dioxide source or the wherein arbitrarily combination of two or more.

In various embodiments, the source of carbon dioxide is carbon dioxide gas or the carbonated solution of packet, institute The metal salt of precipitating is metal carbonate.

In various embodiments, the source of carbon dioxide is carbon dioxide gas or the carbonated solution of packet.

In certain embodiments, the source of carbon dioxide is carbon dioxide gas.

In various embodiments, the source of carbon dioxide be carbon dioxide gas, and in (for example) high-pressure reactor Carbon dioxide gas is mixed with alkaline aqueous solution under pressure (pressure for being greater than atmospheric pressure).

In certain embodiments, the source of carbon dioxide is to wrap carbonated solution.

In various embodiments, carbonated solution is wrapped to be saturated by carbon dioxide.

In other embodiments, the source of carbon dioxide is potential carbon dioxide source.

In various embodiments, potential carbon dioxide source is organic carbonate (such as ethylene carbonate or carbonic acid diformazan Ester).

In various embodiments, the source of carbon dioxide is organic carbonate, and method includes by solution and mixing Organic carbonate heating, to increase the rate that organic carbonate is decomposed into carbon dioxide.

In various embodiments, the method is further contained under agitation and mixes solution with carbon dioxide source.It is described Agitation is preferably high shear.

In various embodiments, metal salt has the solubility less than 0.1g/L at 20 DEG C in water, such as at 20 DEG C Under less than 0.01,0.009,0.008,0.007,0.006,0.005,0.004,0.003 or 0.002g/L.For example, copper carbonate exists There is at 20 DEG C 1.46x10 in water^-5The solubility of g/L, and Kocide SD then has 1.722x 10 at 20 DEG C^-7G/L's Solubility.

In various embodiments, the pH of solution be reduced to pH be about 4.5 to about 10, for example, about 4.5 to 9.5,5 to 10,5 to 9.5,5 to 9,5.5 to 10,5.5 to 9.5,5.5 to 9.

In various embodiments, it is about 4.5 to about 9 that the pH of solution, which is reduced to pH,.

In various embodiments, it is about 6 to about 10 that the pH of solution, which is reduced to pH, for example, from about 6 to 9.5,6 to 9,6.5 to 10,6.5.To 9.5,6.5 to 9,7 to 10,7 to 9.5,7 to 9,7.5 to 10,7.5 to 9.5,7.5 to 9,8 to 10,8 to 9.5 or 8 to 9.

In certain embodiments, it is about 7.5 to about 9.5 that the pH of solution, which is reduced to pH,.

In various embodiments, it is about 8 to about 9 that the pH of solution, which is reduced to pH,.

In various embodiments, providing alkaline aqueous solution includes: providing packet metalliferous alkaline precursor aqueous solution and one Kind or a variety of ligands that can form soluble complexes with metal under alkaline condition；And

Optionally mix one or more dispersing agents.

In various embodiments, providing alkaline aqueous solution includes:

The metalliferous alkaline precursor aqueous solution of packet is provided and one or more can be formed under alkaline condition with metal can The ligand of molten complex compound；And

Mix one or more dispersing agents.

In various embodiments, alkaline solution is provided or alkaline precursor solution is included in comprising alkali (such as sodium hydroxide, hydrogen Potassium oxide, ammonia or amine) aqueous alkalescence medium in by source metal and it is one or more under alkaline condition can with metal formed can The ligand reaction of molten complex compound.

In various embodiments, the alkali be alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide), ammonia or Amine.

In various embodiments, source metal is metallic compound or metal element.In various embodiments, source metal is gold Belong to salt or metal element.In the exemplary embodiment, source metal is metal salt.

In various embodiments, the pH of alkaline solution and/or alkaline precursor solution be at least 9,9.5,10,10.5,11, 11.5,12,12.5,13,13.5 or 14, useful range can be selected from any two in these values, for example, from 9 to 14,9 to 13.5,9 to 13,9 to 12.5,9 to 12,9 to 11.5,9 to 11,9 to 10.5,9 to 10,9.5 to 14,9.5 to 13.5,9.5 to 13,9.5 to 12.5,9.5 to 12,9.5 to 11.5,9.5 to 11,9.5 to 10.5,9.5 to 10,10 to 14,10 to 13.5,10 to 13,10 to 12.5,10 to 12,10 to 11.5,10 to 11 or 10 to 10.5.

In various embodiments, one or more of ligands are selected from the group being made up of: ammonia, amine and glycol, Such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.

In the exemplary embodiment, one or more of ligands are selected from the group being made up of: glycerol, second two Alcohol and ammonia.

In various embodiments, the soluble complexes are-two alcohol complex of metal, metal-ammonia complex or metal- Amine complex.

In various embodiments, described to form complex compound with cognition and metal, it is insoluble under alkaline condition, in neutral pH Under it is unstable.In various embodiments, soluble metal complex compound is decomposed when reducing the pH of alkaline solution.

In various embodiments, the metal is first, second or third transition series metal.

In various embodiments, the metal is nickel, copper or zinc.In the exemplary embodiment, the metal be copper or Zinc.

In the exemplary embodiment, the metal is copper (II) or zinc (II).In certain embodiments, the metal is Copper (II).

In various embodiments, alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition include it is a kind of or A variety of organic solvents.

In various embodiments, one or more organic solvents are miscible with water.In other embodiments, institute It is not miscible with water for stating one or more organic solvents.

In various embodiments, one or more solvents can be at above-critical state.In various embodiments, one or more Solvent can be the supercritical solvent mixed with cosolvent.

In various embodiments, the alkaline aqueous solution comprising subparticle and/or alkaline precursor aqueous solution and/or aqueous group It closes object and further includes one or more surfactants.

In various embodiments, the method is further included by one or more surfactants and comprising subparticle Alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition mixing.

In various embodiments, the method is further included by one or more other dispersing agents and comprising sub-micro Alkaline aqueous solution and/or the water-based composition mixing of grain.One or more other dispersing agents can in alkaline solution It is identical or different through existing one or more dispersing agents.

In various embodiments, the dispersing agent are as follows: anionic dispersing agents, such as polycarboxylate (such as polyacrylic acid Salt), naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, condensate of melamine sulfonate and formaldehyde, alkyl-aryl-group ether phosphate, Or alkyl ether phosphate；Cation dispersing agent；Non-ionic dispersing agent, such as polyethers (including mixed polyethers) or polyvinyl pyrrole Alkanone；Amphoteric ion dispersing agent, such as amphoteric ion polymer；Or the wherein arbitrarily combination of two or more.

In certain exemplary embodiments, the dispersing agent is polyacrylate, polyethers, naphthalene sulphonate formaldehyde condensation Object or the wherein arbitrarily combination of two or more.

In certain exemplary embodiments, the dispersing agent be polyacrylate or polyethers, or combinations thereof.

In various embodiments, the surfactant is: anionic surfactant, such as dodecyl benzene sulfonic acid Salt, lauryl sulfate or lauryl sulfate；Cationic surfactant, such as benzalkonium chloride or cetyl front three Base ammonium bromide；Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol polyoxyethylene ether；Amphoteric ion surface Activating agent；Or the wherein arbitrarily combination of two or more.

In various embodiments, the surfactant is neopelex, lauryl sodium sulfate, lauryl Sodium sulphate, benzalkonium chloride, cetyl trimethylammonium bromide, nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether or its In two or more any combination.

In various embodiments, the method, which is further included, adjusts the alkalinity comprising subparticle by mixed acid or alkali The pH of solution and/or alkaline precursor solution and/or water-based composition.In various embodiments, the method further includes logical Cross the alkaline aqueous solution and/or alkaline precursor aqueous solution and/or water-based composition for adding that the adjusting of sour or alkali includes subparticle pH。

In various embodiments, pH is adjusted by mixed weak acids or weak base.

In various embodiments, pH is adjusted by addition weak acid or weak base.

In various embodiments, pH is adjusted by mixing boric acid and/or borate (such as borax).In various realities It applies in example, pH is buffered by mixing boric acid and/or borate (such as borax).

In certain embodiments, it is about 6 to 10 that the pH of the water-based composition comprising subparticle, which is adjusted to pH, for example, about 6 to 9.5,6 to 9,6.5 to 10,6.5.To 9.5,6.5 to 9,7 to 10,7 to 9.5,7 to 9,7.5 to 10,7.5 to 9.5,7.5 to 9,8 to 10,8 to 9.5 or 8 to 9.In certain embodiments, the pH of the water-based composition comprising subparticle is adjusted to pH and is About 7.5 to 9.5.In certain exemplary embodiments, it is about 8 that the pH of the water-based composition comprising subparticle, which is adjusted to pH, To 9.

In various embodiments, the water-based composition comprising subparticle is at the standard conditions (i.e. in 25 DEG C and atmosphere Under pressure) within 1 day, 2 days, 3 days, 4 days, 5 days, 6 days or 7 days period to cohesion and/or settlement stability colloidal dispersion Body.

In various embodiments, colloidal dispersion is at the standard conditions at least one moon, 2 months, 3 months, 4 months, 5 It is steady to cohesion and/or sedimentation in a month, 6 months, 7 months, 8 months, 9 months, 10 months, 11 months or 12 months period It is fixed.

In various embodiments, it is deposited in and is carried out at a temperature of 0 and 80 DEG C.

In certain embodiments, precipitating carries out at ambient temperature.

In various embodiments, the method is further included the water-based composition concentration comprising subparticle.

In various embodiments, the water-based composition comprising subparticle passes through centrifugal concentrating.

In various embodiments, the water-based composition comprising subparticle is dehydrated to form slurry and/or dry and forms powder End.

In various embodiments, the composition comprising subparticle is biocidal composition.

In certain embodiments, biocidal composition is dispersion, such as colloidal dispersion, it includes mantoquita, zinc salt or The subparticle of a combination thereof.

In the exemplary embodiment, biocidal composition is the dispersion comprising basic copper carbonate subparticle.

In the exemplary embodiment, dispersion is water-borne dispersions.

In various embodiments, biocidal composition, which further includes, one or more helps biocide.

In various embodiments, the composition comprising subparticle further includes one or more biocides.

In various embodiments, biocide is fungicide, insecticide, mildewcide, bactericide or algicide.

In various embodiments, the method is further included by one or more biocides and comprising subparticle Composition mixing.

In various embodiments, biocide is solution, lotion, microencapsulated form, or is subparticle.

In various embodiments, biocide is organic biocide.

In various embodiments, the method includes that mixing includes organic biocide and one or more organic solvents Solution (mixes the composition comprising subparticle and the solution comprising organic biocide and one or more organic solvents It closes).

In various embodiments, organic biocide is: fungicide, including Bravo, iodo propinyl butylamino One of formic acid esters etc. is a variety of；Insecticide, including bifenthrin, decis, Permethrin, imidacloprid etc.；Bactericide Deng；Or mixtures thereof.This list is interpreted as illustrative rather than restrictive.

In various embodiments, the composition comprising subparticle further includes the sub-micro of one or more biocides Particle.

In certain embodiments, the composition includes basic copper carbonate subparticle and Tebuconazole or propiconazole Subparticle or microemulsion or combinations thereof.

In certain embodiments, the composition includes basic copper carbonate subparticle and Bravo subparticle.

In certain embodiments, the composition include basic copper carbonate subparticle and quaternary ammonium compound, tertiary amine or Tertiary amino oxides.

In various embodiments, the composition includes borate and basic copper carbonate subparticle.

In certain embodiments, the composition includes basic copper carbonate subparticle and insecticide (such as bifenthrin) Subparticle.This composition can be used to handle plant, or include in the resin for being used to prepare force fit plate or laminated veneer lumber In.

In various embodiments, the organic solvent comprising organic biocide is miscible in water.

In various embodiments, organic solvent be alcohol (such as C1-6 alcohol), ketone, lactams, glycol ethers or wherein any The combination of two or more.

In various embodiments, C1-6 alcohol be methanol, ethyl alcohol, or combinations thereof.

In various embodiments, the composition comprising subparticle is comprising the metal salt subparticle through pigment coloring Color compositions.

In various embodiments, the subparticle can reflect or absorb the light in visible wavelength region, thus described group It closes object and obtains color.

In various embodiments, the composition comprising subparticle is carbon monoxide-olefin polymeric, and it includes with catalysis characteristics Metal salt subparticle.

In certain embodiments, the method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand, optional one or more dispersing agents and optional one or more weak acid source, wherein the metal is copper (II) or zinc (II), one or more of ligands are selected from ammonia, amine and glycol, so that solvable metal complex is metal-ammino Close object ,-two alcohol complex of metal-amine complex or metal；

Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal salt subparticle precipitating, to provide Water-based composition comprising metal salt subparticle,

Wherein the water-based composition is colloidal dispersion, or is gone flocculation to provide colloidal dispersion.

In certain embodiments, the method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and one or more dispersing agents, wherein the metal is copper (II) or zinc (II), the choosing of one or more of ligands From ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-glycol complexing Object；

The source of solution, carbon dioxide source and optional one or more weak acid is mixed, to reduce the pH of solution, So as to metal salt subparticle precipitating, so that the water-based composition comprising metal salt subparticle is provided,

In certain embodiments, the method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and optional one or more dispersing agents, wherein the metal be copper (II) or zinc (II), it is one or more of Ligand is selected from ammonia, amine and glycol, so that solvable metal complex is metal-ammonia complex, metal-amine complex or metal-two Alcohol complex；

Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal carbonate subparticle precipitating and/ Or metal borate subparticle precipitating, so that providing includes metal carbonate subparticle and/or metal borate sub-micro The water-based composition of particle；

Wherein the water-based composition comprising subparticle is colloidal dispersion, or is gone flocculation to provide colloidal dispersion Body.

In certain embodiments, the method includes:

Solution is mixed with carbon dioxide source to reduce the pH of solution, so as to metal carbonate subparticle precipitating, thus Water-based composition comprising metal carbonate subparticle is provided；And

It include metal hydrogen-oxygen to provide optionally by the water-based composition alkali process comprising metal carbonate subparticle The water-based composition of compound subparticle；And/or

Optionally by the water-based composition comprising metal carbonate subparticle or include metal hydroxides sub-micro The water-based composition heating of grain, to provide the water-based composition for including metal oxide subparticle,

Wherein the water-based composition comprising subparticle (includes the composition of sub-micron metal carbonate particle, includes The composition of sub-micron metal hydroxide particles and/or composition comprising sub-micron metal carbonate particle) it is colloidal state point Granular media, or gone flocculation to provide colloidal dispersion.

In certain embodiments, the method includes:

In various embodiments, the method be in order to generate the metalliferous carbonate of packet, hydroxide, oxide or The composition of the subparticle of borate.

In various embodiments, it includes metal carbonate, metal hydroxides or metal oxygen that the method, which is to generate, The composition of the subparticle of compound.

In various embodiments, when being tested using AWPAE12 Corrosion standards method, the composition and standard ACQ phase At least low by 20% mpy than that can generate, for example, at least low 30%, at least low 40%, at least low 50%, at least low 60%, at least Low 70%, at least low 80% or at least low 90%.In various embodiments, mpy at least low 60%.In another embodiment, The composition will not show corrosion.

On the other hand, the present invention provides through prepared according to the methods of the invention comprising metal salt subparticle Composition.

On the other hand, the present invention provides a kind of method for handling matrix, and the method includes to apply basis to matrix The composition comprising metal salt subparticle of method preparation of the invention.

In various embodiments, the composition passes through dipping, spray, spraying, brushing, mixing or positive pressure dipping, vacuum Pressure impregnation or its modification are applied to matrix.

In various embodiments, by the composition be applied to matrix can assign matrix Biocidal properties, coloring properties or Catalysis characteristics.

In various embodiments, face can be assigned at least one target area of matrix by the composition being applied to matrix Color or hydrophobicity.

In certain embodiments, the processing is to protect matrix from harmful organism organism on matrix or matrix Harmful organism organism is perhaps removed or is prevented harmful organism organism in matrix by interior growth from matrix or in matrix Upper or base tumor growth, or alleviate harmful organism organism on matrix or base tumor growth.

In various embodiments, matrix to be processed is organic matrix.

In various embodiments, described matrix is lignocellulosic matrix.

In other embodiments, described matrix is inorganic matrix, such as concrete or stone.

In various embodiments, the composition is applied to matrix at ambient temperature.

It in various embodiments, is stable under substrate temperature of the composition when applying.

On the other hand, the present invention provides the matrix according to the method processing for handling matrix according to the present invention.

Both as used herein, term "and/or" refers to "and" or "or", or refer to.

Term "comprising" as used in this description refer to " at least partly by ... form.When including term " packet Containing " the specification in explain each narrative tense, before with the term that feature or the feature except those features May exist.The relational language as " including (comprise) " and " including (comprise) " should be explained in the same manner.

The present invention can also widely advocate to include in present specification with two or more in component, element or feature Any combination of kind or the independent component for referring to or pointing out or refer to jointly or point out of all combinations, elements and features, at this Specific integer is referred in text and the integer is in field of the present invention in the case where have equivalent, it is this known Equivalent be believed to comprise herein, it is the same just as individually being illustrated.

It is also all reasonable within the scope of this including referring to be intended to when referring to numberical range (such as 1 to 10) disclosed herein Numerical value (such as 1,1.1,2,3,3.9,4,5,6,6.5,7,8,9 and 10), and further include referring to reasonable value within the scope of this Any range (such as 2 to 8,1.5 to 5.5 and 3.1 to 4.7), therefore, clear disclosed all ranges is all herein Subrange is specifically disclosed herein.These examples being only especially desired to, between cited minimum and peak The all possible combinations of numerical value should all be counted as clearly stating in a similar way in this application.

Although the present invention is carrying out the definition of wide scope above, it will be understood by those skilled in the art that the present invention is not It is confined to this, the invention also includes each embodiments, are described below and provide the example.

Detailed description of the invention

The description present invention with reference to the drawings, in the accompanying drawings:

Fig. 1 is the photo of the sample of the copper carbonate subparticle dispersion prepared in example 1, shows that the dispersion is It is optically transparent.

Fig. 2 is the photo of the sample of the copper carbonate subparticle dispersion prepared in example 1, and display is when LED light source Light beam passes through the muddiness observed when sample.

Fig. 3 is the chart for showing the particle size distribution of the dispersion formed in example 1.

Fig. 4 is the scanning electron micrograph (SEM) of the dispersion granule formed in example 7.

Specific embodiment

Inventors hereof have unexpectedly found that subparticle biocide, pigment and catalyst can be simple and have Effect ground from optionally including the metal complex alkaline aqueous solution precipitating of one or more dispersing agents by preparing.

Device and the device fabrication of simple cheap can be used not to lead without the use of expensive milling apparatus for subparticle High-energy cost or cooling cost are caused, the solvent or surfactant of large volume are not needed yet.Subparticle is convenient to connecing It is manufactured closely or in lesser manufacturing cell positioned at final field of employment.

The Biocidal composition prepared by wet grinding, especially subparticle composition, it is necessary to be generated concentrating on Large volume is prepared in the manufacturing cell to minimize cost, and composition of the invention then can field of employment simply and economically It generates.

Therefore, in one aspect, the method for the composition the present invention relates to preparation comprising metal salt subparticle.Substantially and Speech, the method comprise the steps of:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and optional one or more dispersing agents；And

On the other hand, the method for the composition the present invention relates to preparation comprising metal salt subparticle, the method Include:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with metal under alkaline condition Ligand and one or more dispersing agents；And

As used herein, term " subparticle " refers to that particle does not all have in any side more than or equal to 1 micron Size.As used herein, term " particle size " refers to the size of the maximum dimension of particle.

Technology well known by persons skilled in the art can be used to measure for particle size, such as laser diffraction, photon correlation spectroscopy Method, sedimentation field flow fractionation, disk centrifuge filtration method or inductor section.In various embodiments, " subparticle " has at least 0.005 Micron and the particle size less than 1 micron, for example, at least 0.01 micron and less than 1 micron.Water comprising metal salt subparticle Property composition may include with the particle greater than 1 micron of particle.But in certain embodiments, existing this particle Amount is preferably lower, is, for example, less than 30%, 20%, the 10% of particle or is greater than 1 micron less than the 5% of particle.

Metal can be the transition metal selected from first, second or third transition series.Metal may be at any suitable Oxidation state.In the exemplary embodiment, metal is zinc or copper, such as Zn (II) or Cu (II).

The method can be used to provide comprising various different metal salt (such as the carbonate of metal, hydroxide, oxidation Object and borate) subparticle composition.

In certain embodiments, metal salt be copper carbonate, Kocide SD, copper oxide, copper borate, zinc carbonate, zinc hydroxide, Zinc oxide or zinc borate.In certain embodiments, metal salt is copper carbonate, Kocide SD, copper oxide, zinc carbonate, hydroxide Zinc or zinc oxide.In certain embodiments, metal salt is copper carbonate, Kocide SD, copper oxide or zinc carbonate.In certain demonstrations In the embodiment of property, metal salt is basic copper carbonate.In other exemplary embodiments, metal salt is zinc carbonate.

It can be provided in the form of streaming flow the composition comprising subparticle prepared by the method, such as colloidal state Dispersion, slurry or powder.Also granule can be converted by the composition.In certain embodiments, the composition is to have The aqueous fluids form of active component provides, and the component is non-volatile at the temperature at which application.

In order to provide slurry or powder, the water-based composition comprising subparticle can be concentrated, to reduce in composition The amount of liquid.The composition can be concentrated by various modes, including centrifugation, filtering, dialysis, infiltration, electrophoresis etc..Picture chlorine, Soluble ion as nitrate anion, sulfate radical, sodium, potassium etc. can be removed by dialysis or by centrifugation and washing.Concentration can relate to And it is dehydrated to form slurry, and/or be related to dry to form powder.

The composition can provide in the form of dispersion.Unless otherwise noted, otherwise as used herein term " divides Granular media " refers to a kind of homogeneous (uniform) fluid or powder, and wherein metal salt subparticle is evenly dispersed in entire powder or fluid.

In certain embodiments, the water-based composition comprising subparticle is colloidal dispersion.The dispersion includes packet Include the aqueous continuous phase and discontinuous phase of metal salt subparticle.Colloid or colloidal dispersion are generally comprised with about 1 to about The particle of 1000 nanometers of particle size.Transparent colloid usually has particle of the particle size less than 700 nanometers.The presence of colloid It can be determined by observation Tyndall effect.In Tyndall effect, the light of light beam is when light beam passes through colloid by colloid Particle scattering, otherwise it is sightless (such as Fig. 1 and seen in fig. 2) for naked eye.

The water-based composition may include flocculated metal salt subparticle.In such an embodiment, the method can be into One step includes the step of the composition is gone flocculation, to provide colloidal dispersion.Go flocculation (or peptization) that can pass through Any suitable way carries out, such as by carrying out ultrasonic treatment to composition or dilute composition, for example, with liquid phase its The dilution of its component (such as other water or dispersing agent).Go flocculation that can also carry out by mixing one or more deflocculants.

The composition can be concentration form or use formulation form, such as be suitble to directly be applied to matrix (example Such as timber) composition.In various embodiments, concentrate includes by weight of the composition about 0.1 to 30% water, Such as by weight of the composition 0.1 to 25,0.1 to 20,0.1 to 15,0.1 to 10,0.1 to 5,0.5 to 30,0.5 to 25,0.5 to 20,0.5 to 15,0.5 to 10,0.5 to 5,1 to 30,1 to 25,1 to 20,1 to 15,1 to 10 or 1 to 5% water, And useful range can be selected from any two in these values.In various embodiments, i.e., with formulation comprising pressing described group Close object poidometer about 80 to 99.5% water, such as by weight of the composition 85 to 99.5,90 to 99.5 or 95 to 99.5% water, and useful range can be selected from any two in these values.

The amount of metal salt can change according to target application in the composition.In various embodiments, the composition Comprising based on the dry weight of the composition about 50 to 95% metal salt, such as based on the dry weight of the composition 50 to 90,50 To 85,50 to 80,50 to 75,55 to 95,55 to 90,55 to 85,55 to 80,55 to 75,60 to 95,60 to 90,60 to 85,60 To 80,60 to 75,65 to 95,65 to 90,65 to 85,65 to 80,65 to 75,70 to 95,70 to 90,70 to 85,70 to 80 or 70 to 75% metal salt, and useful range can be selected from any two in these values.

Water-based composition may include one or more organic solvents and/or one or more surfactants.Organic solvent It can be polar, nonpolar, miscible with water or not miscible with water.

The composition can be the biocidal composition comprising biocidal metal salt subparticle.Biocidal of the invention Composition can contain polarized and/or nonpolar solvent etc., or contain surfactant or dispersing agent, so as to when needed for most Whole Biocidal composition assigns specific characteristic.It will be understood by a person skilled in the art that various combinations of the invention can be applied to Object.

By way of example, impregnation of timber can pass through the various vacuum or pressure of the fluid containing biocide of the invention Power is realized.Alternatively, the fluid for containing biocide of the invention can be sprayed to plant.There is hydrophobic property in desired matrix Or in the case where different colours, composition may include that or can be used containing certain for making those of water-proofing treatment to matrix The composition of dyestuff or pigment, to paint to matrix.

Alternatively, the composition can be color compositions or carbon monoxide-olefin polymeric.Color compositions include through face Expect the subparticle of the metal salt of coloring.Carbon monoxide-olefin polymeric includes the metal salt subparticle with catalysis characteristics.

Suitable pigment includes but is not limited to green copper carbonate, white zinc carbonate, light green color nickelous carbonate, black oxidation Copper and green copper borate.All these salt are used equally for ceramics, also act as catalyst.It may include this in timber preservative Kind pigment, to enhance the color of handled timber.

Transition metal oxide is used as catalyst.Example includes nanoparticle copper oxide and nickel oxide, is used for methanol Catalysis oxidation.It with the catalyst of hydrogen reacted include zinc oxide and copper oxide for carbon monoxide.The oxidation of nanoparticle metal Object can be prepared by heating metal carbonate as described herein.

It can be stabilization for agglomerating and/or settling in the water-based composition comprising subparticle of colloidal dispersion form 's.Dispersion at the standard conditions-i.e. under environment temperature (25 DEG C) and atmospheric pressure 1 day, 2 days, 3 days, 4 days, 5 days, 6 It or 7 days or 1 month, 2 months, 3 months, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months, 11 It can be in the period of the moon or 12 months stable.

One or more dispersing agents may be present in the composition, to stablize subparticle without (for example) settling And/or aggregation.The amount of dispersing agent, the type of dispersing agent and addition opportunity can be used to adjust the particle size of the composition and steady It is qualitative.

The water-based composition may include one or more dispersing agents.Any proper amount of point may be present in the composition Powder.In various embodiments, one or more dispersing agents are can effectively provide stable water-based composition colloidal dispersion Amount exists.

In various embodiments, the composition comprising subparticle includes about 5 to 50% based on the dry weight of the composition One or more dispersing agents, such as based on the dry weight of the composition about 5 to 45,5 to 40,5 to 35,5 to 30,5 to 25,5 To one kind of 20,5 to 15,10 to 50,10 to 45,10 to 40,10 to 35,10 to 30,10 to 25,10 to 20 or 10 to 15% Or a variety of dispersing agents, and useful range can be selected from any two in these values.In various embodiments, the composition Include based on the dry weight of the composition about 5 to 50% one or more dispersing agents.

The dispersing agent can be known to the skilled in the art a series of one of dispersing agents.The dispersing agent can To be organic dispersing agent, anionic dispersing agents, cation dispersing agent, non-ionic dispersing agent or amphoteric ion dispersion can be Agent.In some embodiments, the dispersing agent is polymer, such as anionic polymer, cationic polymer, non-ionic polymeric Object or amphoteric ion polymer.For example, the dispersing agent may is that anionic dispersing agents, such as polycarboxylate, naphthalene sulfonate Formaldehyde condensation products, ligninsulfonate, condensate of melamine sulfonate and formaldehyde, alkyl-aryl-group ether phosphate or alkyl ether phosphates Salt；Cation dispersing agent；Or non-ionic dispersing agent, such as polyethers (including mixed polyethers) or polyvinylpyrrolidone；Or Person's amphoteric ion dispersing agent, such as amphoteric ion polymer；Or the wherein arbitrarily combination of two or more.Cation dispersion The example of agent include but is not limited to dialkyl amido replace acrylates, such as dimethylamino replace acrylates, Polyethyleneimine etc..Anionic dispersing agents may include sulfate radical, sulfonate radical, phosphonate radical, phosphate radical or carboxyl.

The composition also may include one or more surfactants.One or more surfactants can be into one Step stablizes the subparticle in the composition.Surfactant can be carried out according to the compatibility of one or more dispersing agents Selection.

Any suitable surfactant can be used.Surfactant can be organic surface active agent, can be yin Ionic surface active agent, cationic surfactant, nonionic surfactant or zwitterionic surfactant.Example packet It includes (but being not limited to): anionic surfactant, such as dodecyl benzene sulfonate, lauryl sulfate or dodecyl sulphur Hydrochlorate；Cationic surfactant, such as benzalkonium chloride or cetyl trimethylammonium bromide；Nonionic surfactant, example Such as polyvinylpyrrolidone, nonylphenol polyoxyethylene ether or octyl phenol polyoxyethylene ether；Zwitterionic surfactant etc..

Other than metal salt subparticle (it can be biocidal), the composition also may include one or more Biocide.It may include biocide and/or help biocide to realize specific purpose, such as to expand the composition controllable The organism range of system.

Composition comprising metal salt subparticle can be with one or more solution, lotion, microencapsulation or subparticle The biocide of form mixes.The biocide of solution form may include biocide and one or more organic solvents.

The example of biocide includes but is not limited to fungicide, insecticide, mildewcide, bactericide, algicide Deng.Biocide can be organic biocide or inorganic biocidal agent, such as borate.

Organic biocide is well-known to those skilled in the art, and including (for example) pyrrole, Quaternary ammonium compound, fluorinated compound and combinations thereof.Organic biocide may is that fungicide, including Bravo, iodopropynyl One of base butyl carbamate, quaternary ammonium compound, triazole compounds etc. are a variety of；Insecticide, including bifenthrin, bromine Cyano chrysanthemate, Permethrin, imidacloprid etc.；Bactericide etc.；Or mixtures thereof.

Biocide can be water-soluble or water-insoluble.The example of water soluble biocide includes quaternary ammonium compounds Object, such as zephiran, dimethyl didecyl ammonium chloride, dimethyl didecyl ammonium carbonate/dimethyl didecyl Base ammonium hydrogen carbonate etc..The example of water-insoluble biocide includes but is not limited to: pyrrole, for example, Cyproconazole, propiconazole, Tebuconazole, (TCMTB), 2- (Extraction kinetics sulfydryl), benzothiazole, Bravo and Euparen；Isothiazolone, such as Kathon930, KathonWT, methylisothiazolinone, benzisothiazole-3-ketone and 2- octyl -3- isothiazolone；Pyrrole Worm quinoline；Butylamino formic acid iodine propine base ester (IPBC)；Pyrethroid, such as bifenthrin, cypermethrin and chlorine chrysanthemum Ester；Poison barnyard grass with poison；4- cumyl phenol；Fipronil；Carbendazim；Cyfloxylate；And 4- α-cumyl phenol.

In various embodiments, biocide is fungicide.In various embodiments, fungicide is selected to the wooden rotten load The group of the active fungicide of daughter bacteria.In various embodiments, fungicide includes raw selected from the pure and mild ergosterol of azoles One or more fungicides of the group of object synthetic inhibitor, to prevent the growth of white rot, brown rot and soft rotten fungi, it is not In the timber of processing the main reason for decay of wood.The example of azoles alcohol includes Climbazole, clotrimazole, imazalil, dislikes imidazoles, miaow Fresh amine, fluorine bacterium azoles, oxygen ring azoles, bromuconazole, cyproconazole, diclobutrazol, Difenoconazole, olefin conversion, Da Keli, epoxiconazole, second ring Azoles, benzoxazole, Fluquinconazole, Flusilazole, Flutriafol, furconazole, furconazole_cis, hexaconazole, amide azoles, kind bacterium azoles, the special seat that goes out, nitrile bacterium Azoles, penconazole, propiconazole, prothioconazoles, quinconazole, simeconazoles, Tebuconazole, tetraconazole, triazolone, Triadimenol, Triticonazole, uniconazole P and Dan Kesu.The example of ergosterol biosynthesis inhibitor includes morpholine fungicide, such as two Methyl morpholine, benzamorph, carbamorph, dimethomorph, dodemorfe, butadiene morpholine, flumorph and tridemorph.It was found that can The example for effectively antagonizing other fungicides of one or more domestomycetes include carboxin, iprodione, fenpiclonil, Fu Erbang, Fenpiclonil, bacterium pellet, 8-hydroxyquinoline, Dithane A40, oxycarboxin, cyprodinil, Bravo, Fluoxastrobin, trifloxystrobin, Fu Mei Double, fluazinam, kobam, carbendazim and benomyl.These fungicides can in the present invention with one or more azoles alcohol or Ergosterol biosynthesis inhibitor is applied in combination.

In various embodiments, biocide is insecticide.The example of insecticide include pyrazoline, indazole, oxidation indazole, Pyrazoline carboxanilides, pyridazine, oxadiazines, tricyclic pyridazine, tricyclic oxadiazines, tricyclic triazine, carbaminate, organic phosphate (such as poisoning barnyard grass and DDVP with poison), fenvalerate, Fipronil and indoxacarb and its metabolin and its mixture.

The optional consisting of antifungals of biocide, such as include group below: benzimidazole；Substituted morpholine；Triazole, It may include propiconazole, Tebuconazole, hexaconazole and other triazoles etc.；Diazole may include Prochloraz, phthalocyanine, quaternary ammonium compound, different Thiazolinone, Guanoctine, dodine, di-2-ethylhexylphosphine oxide thiocyanates, o-phenyl phenol etc.；Tertiary amino oxides, such as alkyl-dimethyl Base amine oxide；Fungicide containing iodine etc..Biocide can be selected from insecticide, such as synthetic pyrethroid (such as fluorine chlorine chrysanthemum Ester, decis, Permethrin etc.) or imidacloprid group.Those skilled in the art will be appreciated that other suitable selections.Many is killed Biological agent is all known to those skilled in the art, including is used for those of wood preservation or agricultural.

In various embodiments, one or more biocides include quaternary ammonium compound, boron compound, fluorinated compound Object or pyrrole.

In various embodiments, quaternary ammonium compound is that benzene pricks ammonium salt or dimethyl didecyl ammonium salt.In various embodiments, Quaternary ammonium compound is benzalkonium chloride or dimethyl didecyl ammonium chloride.In various embodiments, quaternary ammonium compound is didecyl two Methyl carbonic acid ammonium or didecyldimethylammonium ammonium bicarbonate.

In one embodiment, pyrrole is propiconazole or Tebuconazole or combinations thereof.

In one embodiment, one or more biocides are the desinsection as Permethrin or Biphenthrin Agent, or the fungicide as Bravo.

In one embodiment, the composition includes amine oxide or alkoxylated amine, can help to biocidal Distribution of the agent in matrix (such as timber).

The biocide with low solubility can be used as micronized particle, as lotion or microemulsion in the composition Or it is introduced as encapsulated or microencapsulation particle.In various embodiments, the composition includes subparticle biocidal The microemulsion of agent, biocide or microencapsulation biocide.

Although being not intended to be bound by any particular theory, the inventor believes that in the method for the invention, making Cause to precipitate when reducing the pH of the alkaline aqueous solution of the metal comprising soluble complexes form with carbon dioxide source, to generate gold Belong to compound subparticle.In certain embodiments, the metal in alkaline aqueous solution is converted carbonate by carbon dioxide.Cause Solution is mixed the pH that can reduce solution in various embodiments by this with carbon dioxide source, so as to metal carbonate subparticle Precipitating.

In various embodiments, solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal borate Asia Microparticle precipitating.It include borate ion by its aqueous solution for precipitating subparticle in some this embodiments.It is some this In kind of embodiment, metal carbonate subparticle and metal borate subparticle can precipitate and/or metal carbonate and The subparticle of metal borate can precipitate.

Metal salt subparticle includes metal salt.It should be understood that a other metal salt subparticle may include other co-precipitation Component.For example, in some embodiments, metal borate subparticle may include an other subparticle, and it includes metals The metal carbonate of the co-precipitation of borate and a certain amount.

In some embodiments, the subparticle is made of metal salt or is substantially made of metal salt.For example, In some embodiments, metal carbonate subparticle is made of metal carbonate or is substantially made of metal carbonate.? In some embodiments, metal salt subparticle include based on the weight of the particle at least 75,80,85,90,95,97,98,99, Or 100% metal salt.

Metal complex is soluble under the alkaline condition of alkaline solution, but in certain embodiments under neutral ph It is unstable.Soluble metal complex compound is decomposable when reducing the pH of alkaline solution by mixing carbon dioxide source.Solvable gold Belonging to complex compound can be decomposed by the carbon dioxide reaction provided with carbon dioxide source.For example, one of soluble metal complex compound or Multiple ligands can as described herein and carbon dioxide reaction.

One or more ligands of soluble metal complex compound can be by the decomposition of soluble metal complex compound from soluble metal network Close object release.Alternatively or in addition, the salt of one or more ligands of soluble metal complex compound can pass through soluble metal The decomposition of complex compound generates.In certain embodiments, pass through one or more ligands of the decomposition release of soluble metal complex compound For glycol.In certain embodiments, the salt of the one or more ligand generated by the decomposition of soluble metal complex compound is carbon The carbonate of sour ammonium (ligand is ammonia) or amine (ligand is amine).This salt can pass through ammonia ligand or amine ligand and chemistry The reaction of the carbon dioxide of calculation amount generates.

Without wishing to be bound by theory, inventor believes the one or more ligands discharged or passes through soluble metal Its salt that the decomposition of complex compound generates can reduce or prevent the aggregation and/or sedimentation of subparticle.As such, one discharged Or multiple ligands or its generated salt potentially act as deflocculant to stablize subparticle.

Although it is generally desirable to by cost minimization to which use must for formation soluble metal complex compound as described herein The one or more ligands for the minimum stoichiometric amount wanted, but excessive ligand can be used in certain embodiments.Obviously, alkali Property aqueous solution and/or its salt (such as by being generated with carbon dioxide reaction) in there are this excessive (or free or not Coordination) ligand can also reduce or prevent aggregation and/or sedimentation of the subparticle in water-based composition.

Reaction can carry out under optimal conditions, be formed by subparticle to maximize.However, it is understood that certain In embodiment, the water-based composition may include unreacted raw material, such as the undecomposed soluble metal complex compound of trace.

Alkaline aqueous solution is mixed with carbon dioxide source to carry out under vigorous agitation, although stirring in some embodiments Need not be violent.Those skilled in the art stir required for being readily determined according to the property and processing conditions of reactant Traverse degree.Vigorous agitation can be provided by mixer, ultrasonic treatment of high speed agitator, commonly referred to as Silverson etc..Agitation It can be high shear agitation.

Carbon dioxide source provides carbon dioxide for aqueous solution.According to used source, carbon dioxide can be introduced directly into instead In answering or original position generates.Any suitable carbon dioxide source can be used.In various embodiments, carbon dioxide source is titanium dioxide Carbon gas wraps carbonated solution or potential carbon dioxide source.

Carbon dioxide gas under agitation can be mixed gas sparging by alkaline solution by (for example) with alkaline solution. In various embodiments, carbon dioxide gas can be molten with alkalinity under stress in suitable reactor (such as high-pressure reactor) Liquid mixing.In mixing under stress (i.e. under the pressure for being greater than atmospheric pressure, so that carbon dioxide is remained liquid condition) In some embodiments carried out in the suitable reactor (such as high-pressure reactor), can also use liquid CO 2 as Carbon dioxide source.

Wrapping carbonated solution can be saturated by carbon dioxide.Wrapping carbonated solution can be aqueous solution.This Kind solution can be prepared at low temperature, to increase the amount for dissolving in the carbon dioxide in the solution.Preparation packet is carbonated The method of solution will be apparent to those skilled in the art.

Potential carbon dioxide source includes that can (for example) decompose to provide the organic carbon of carbon dioxide at reaction conditions Acid esters, such as ethylene carbonate or dimethyl carbonate.It, can will be anti-in order to increase the rate that organic carbonate is decomposed into carbon dioxide Mixture is answered to heat.

Carbon dioxide source can be mixed with controllable rate with solution, such as slowly be mixed with solution, to obtain desired pH.It can PH is monitored during mixing step.

Solution can be mixed with carbon dioxide source at any suitable temperature (such as from 0 to 80 DEG C temperature), with drop The pH of low alkalinity solution, so as to metal salt subparticle precipitating.Advantageously, it can sink at ambient temperature in certain embodiments It forms sediment.

Solution is mixed to the pH that can reduce solution with carbon dioxide source, so as to metal carbonate subparticle precipitating.

Alkaline aqueous solution can further include the source of one or more acid, such as the source of one or more weak acid.? In some embodiments, can before forming soluble metal complex compound, in the process or rear one or more acid are introduced into solution Source, such as the source of one or more weak acid, as long as one or more acid will not interfere soluble metal complex compound It is formed or decomposes soluble metal complex compound.In certain embodiments, can mix one or more optional dispersing agents it Before, mix one or more acid in the process or later.In some embodiments, before the one or more sour and alkalinity The mixing of body aqueous solution.

In some embodiments, the method may include in any order by solution, carbon dioxide source and a kind of or more The source mixing of kind acid.One or more acid can be weak acid.Weak acid is the acid that only can partially dissociate in aqueous solution. I.e. only some weak acid can discharge its proton in the solution.In contrast, strong acid can then will be completely dissociated in aqueous solution.Acid Acid ionization constant (Ka) shows the degree that acid dissociates in the solution.Acid ionization constant can be expressed as pKa.Weak acid, which can be, to be had extremely The weak acid of few about 6 pKa.Weak acid can be the weak acid that salt essentially insoluble in the water of pH7 can be formed in metal.Ying Li It solves, the subparticle formed in this embodiment of the method may include the metal salt of weak acid.

The example of weak acid includes but is not limited to boric acid and phenol, such as o-phenyl phenol, phenol, cresols, xylenol, hundred In fragrant phenol etc..Weak acid source is boric acid or borate, such as borax in certain exemplary embodiments.

The metal salt precipitated in the method is substantially insoluble in.Metal salt can have molten less than 0.1g/L and 20 DEG C Xie Du.Metal salt preferably has less than 20 DEG C of 0.01g/L of solubility.

For example, being used to that timber or the biocide of plant is protected once to apply usually has low solubility.Otherwise work as exposure They can be lost in environment when being exposed to water (such as rainwater).Certain this biocides there is low solubility but be enough by The intake such as insect, fungi.Example includes that Ksp (solubility product in water) is 1.4 × 10^–10Copper carbonate, Ksp be 1.4 × 10^–11's Zinc carbonate and Ksp are 2.2 × 10^–20Kocide SD.

In the case where the composition includes metal carbonate subparticle, the method can further include will be described Composition alkali process, to convert metal hydroxides subparticle for metal carbonate particles.Converting the alkali used can To be alkali or alkaline earth metal hydroxide.Reaction can be carried out advantageously at ambient temperature.

In the case where the composition includes the subparticle of metal carbonate or metal hydroxides, the method can It further includes and heats the composition, to convert metal oxygen for metal carbonate particles or metal hydroxide particle Compound subparticle.The composition can heat at any suitable temperature, such as from about 50 to about 95 DEG C of temperature.At certain In a little exemplary embodiments, the composition about 80 DEG C at a temperature of heat.

The method can further include the water-based composition of the subparticle generated when being included in the pH for reducing solution With one or more dispersing agents or other dispersing agent and/or one or more surfactants or other surface-active Agent mixing, to increase the stability of subparticle in the composition, such as the stability to sedimentation and/or cohesion.

According to the target application of the composition, the method be can further include by mixing one or more acid or alkali (such as weak acid or weak base) adjusts the pH of the composition comprising subparticle.Mixed acid or alkali may act as pH buffer. In some embodiments, pH is adjusted by mixing one or more acid and one or more alkali.

In certain embodiments, the pH of the composition can be adjusted by mixing boric acid and/or borate (such as borax). In some embodiments, adding borate (such as after forming precipitating) can produce the combination containing free borate ion Object.Therefore in some embodiments, water-based composition includes borate ion.

As described in each example, inventor's discovery uses borax as buffer, and the pH of the composition can be adjusted to About pH9.Sodium tetraborate (borax) or corrosion inhibitor, therefore the corrosiveness of the composition can be reduced.

It is about 6 to about 10 that the pH of the composition, which can be adjusted to pH,.In some embodiments, the water-based composition It is about 7.5 to about 9.5, for example, about 8 to 9 that pH, which can be adjusted to final pH,.PH can be monitored (simultaneously in the pH adjustment process And can be monitored in any other step as described herein that pH is changed).The appropriate method of pH is monitored for this field It is known for technical staff.

In some embodiments, the pH of alkaline solution be reduced to a certain pH (such as pH is about 7.5 to 9.5, for example, about 8 to 9), so as to metal salt subparticle precipitating, to form the water-based composition of this pH, it includes have to be suitble to target application The subparticle of pH.In such an embodiment, no subsequent pH adjustment step may be necessary.

Without wishing to be bound by theory, inventor believes at the pH from about 7.5 to about 9.5 (for example, about from 8 to 9), The solubility of the metal salt (such as copper carbonate) precipitated is low.In addition, inventor believes the corruption of the composition at this pH Erosion effect is also low, this is because the ionic metal in solution is seldom.This pH may further be used to reduce or minimize metal (such as Copper) from the leaching and/or loss of the matrix (such as timber and other lignocellulosic matrixes) through the compositions-treated.

It for example, in certain embodiments, the composition can have the pH from about 8 to 9, and include basic copper carbonate form Mantoquita subparticle.

Inventors have found that at least can have low corruption by the water-based composition that the method generates in certain embodiments Erosion effect.In various embodiments, when being tested using AWPAE12 Corrosion standards method, the composition is compared with standard ACQ At least low 20% mpy can be generated.Although AWPAE12 Corrosion standards method may not specify the amount for being added to the copper of timber, But those skilled in the art will be appreciated that typical introduction volume, and also it will be appreciated that higher loading capacity can proportionally make to corrode Deteriorate.Any suitable standard ACQ can be used to compare.In some embodiments, standard ACQ is A type, Type B, c-type or D Type.It is compared in certain preferred embodiments with Type B ACQ.

Alkaline aqueous solution includes metal, one or more can form soluble complexes with metal under alkaline condition and match Body and optional one or more dispersing agents.Although the presence of one or more dispersing agents can be used in some embodiments Stablize and be formed by subparticle, but inventor's discovery at least presence of one or more dispersing agents in some embodiments is not It is necessary.Without wishing to be bound by theory, inventor believe be formed by subparticle in such an embodiment can be by such as Other components present in composition as described herein are stabilized without assembling and/or settling.

Can by provide comprising metal and it is one or more under alkaline condition can with metal formed soluble complexes The alkaline precursor aqueous solution of ligand, and one or more dispersing agents are optionally mixed, to provide alkaline aqueous solution.In certain realities It applies in example, two or more different dispersing agents can concurrently or consecutively be mixed with precursor solution.

Alkaline aqueous solution can further include one or more surfactants.One or more surfactants can It is mixed before or during optionally mixed dispersant with precursor solution, or is optionally mixing one or more dispersing agents It is mixed later with alkaline solution.

The pH of alkaline solution or precursor solution can be adjusted when required by mixed acid or alkali, such as optionally mixed Before dispersing agent or before mixing carbon dioxide source.

Alkaline solution and precursor solution also may include one or more organic solvents as described herein.

Alkaline solution comprising soluble metal complex compound can have at least 9 pH, for example, at least 9.5,10,10.5,11, 11.5,12,12.5,13,13.5 or 14, and useful range can be selected from any two in those values.Basicity can be by alkali hydrogen Oxide, ammonia or amine contribution.

The pH of alkaline solution is lowered in the method, so as to metal salt subparticle precipitating.The pH of alkaline solution can Being reduced to pH is 4.5 to about 10, for example, about 4.5 to about 9, for example, about 5 to 9,5.5 to 9,6 to 9,6.5 to 9 or 7 to 9.At certain In a little embodiments, it is about 6 to about 9 that the pH of alkaline solution, which is reduced to pH,.In other embodiments, the pH of alkaline solution can be reduced to PH is about 6 to about 10, for example, about 7.5 to 9.5.In certain exemplary embodiments, it is about 8 that the pH of alkaline solution, which is reduced to pH, To 9.

In certain embodiments, the method includes that metal salt subparticle is deposited to matrix (example from alkaline aqueous solution Such as the particle of carbon, silica or clay, it is also possible to subparticle) on.

Alkaline aqueous solution or precursor solution can by the aqueous alkalescence medium comprising alkali by source metal and a kind of or more Kind can form the ligand reaction of soluble complexes with metal to prepare under alkaline condition.Reaction can be at any suitable temperature It carries out, such as 5 to 95 DEG C, 10 to 90 DEG C or 20 to 50 DEG C.Advantageously, in various embodiments, reaction can be at ambient temperature It carries out.

Being formed by soluble complexes can be-two alcohol complex of metal, metal-ammonia complex or metal-amine complexing Object.The ligand for forming this soluble complexes includes but is not limited to ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and more First alcohol.

The alkali for providing the alkaline condition for forming soluble complexes can be alkali metal hydroxide (such as sodium hydroxide or hydrogen Potassium oxide), ammonia or amine.When ligand is ammonia or amine, the ligand can also serve as alkali in the reaction.

It can be metallic compound or metal element with the source metal of one or more ligand reactions.Source metal is usually solid Body is dissolved with when one or more ligand reactions under alkaline condition.Metallic compound can be metal salt, such as carbonic acid Copper, Kocide SD, copper oxide, zinc carbonate, zinc hydroxide or zinc oxide.In another example, metal salt can be boric acid Copper.Metal element can be elemental copper, (for example) react with ammonia and carbonate is reacted with oxygen (or oxygen in air) When dissolve.

Various metals (such as metal of First Transition series) are capable of forming metal-ligand network as known to those skilled in the art Close object.

The metal complex formed in method of the invention can be metal-ammonia complex or metal-amine complex.In gold In category-ammino-complex, metal and at least one ammonia (or ammonate) ligand complex.For example, cuprammonium is with formula Cu (NH₃)₄ ²⁺ Copper-ammino-complex.The charge 2+ of the complex compound is by one or more suitable anion balances, such as by carbonate anion Balance obtains carbonic acid cuprammonium, or is balanced to obtain boric acid cuprammonium by borate.Carbonic acid cuprammonium is cationic octahedral complex.Gold The other examples of category-ammino-complex include Co (NH₃)₄、Zn(NH₃)₆With Ni (NH₃)₆。

The metal of many First Transition series forms tetrammine.The metal of second, third and the 4th transition series can Form similar compound.It is some to will form alternative complex compound, such as silver, it will form two ammino-complexes.Copper and mickel can (for example) form hexmmine.

The subparticle dispersion of the salt of these metals or its oxide or hydroxide can be used for each as described herein Kind application.In certain embodiments, method of the invention provides the advantageous manner for obtaining this dispersion.

In certain embodiments, metal complex is copper tetrammine；Cu(NH₃)₄ ²⁺.The metal in this complex compound It there may come a time when with the chemical ratio of ligand critically important to solubility.For example, Cu (NH₃)₄ ²⁺With high-dissolvability, and Cu (NH₃)₂ ²⁺Then Do not have.Similarly, Ag (NH₃)₂ ²⁺With high-dissolvability, and Ag (NH₃)²⁺Do not have then.

In the embodiment of the present invention method, the stoichiometric ratio of ligand and metal, which to be formed by complex compound, to be dissolved in In alkaline aqueous solution.In some embodiments that wherein metal is copper, copper: ammonia stoichiometric ratio can be about 1:4.In some realities It applies in example, it will during the carbon dioxide and ligand reaction formation metal salt subparticle by providing carbon dioxide source The ratio of metal and ammonia ligand changes.It should be understood that this high-caliber ammonia can lead to when the ratio of copper and ammonia ligand is 1:4 PH is got higher.When controlledly adding carbon dioxide, pH is lowered, and ammino-complex decomposes, and forms submicron particles.

In metal-amine complex, metal and at least one amine are complexed.The example of suitable amine includes but is not limited to single Ethanol amine, diethanol amine, triethanolamine, ethylenediamine etc..

Metal can change with the stoichiometric ratio of amine or ammonia according to the ratcheting degree of metal and amine.For example, as ethylenediamine this The bidentate ligand of sample can occupy two co-ordination positions of metal.In various embodiments, the stoichiometric ratio of metal and ammonia or amine For at least about 1:1 to 1:6.In certain exemplary embodiments, the stoichiometric ratio of metal and ammonia is at least 1:4.

In various embodiments, alkaline solution and/or precursor solution include metal ammine complex or metal amine complexes, The ammonia or amine of middle complex compound are provided by ammonia or amine, wherein pH be at least 9, for example, at least 9.5,10,10.5,11,11.5,12, 12.5,13,13.5 or 14, and useful range can be selected from any two in these values.

Ammonia metal complex or amine metal complex can be prepared by reacting metal salt with ammonia or amine, be formed octahedra Complex compound.In one embodiment, metallic compound and ammonia or amine understand self alkalization (such as ammonia), form ammino-complex or amine Complex compound.Prepare ammonia metal complex or amine metal complex other methods will be to those skilled in the art it is aobvious and It is clear to.

Metal complex can be-two alcohol complex of metal, this complex compound be metal and one or more glycol (such as 1,2 glycol, such as glycerol or 1,3 glycol, such as 1,3 propylene glycol) complex compound.- two alcohol complex of metal herein may be used Referred to as metal glycol compound.

The preparation of-two alcohol complex alkaline solution of metal is PCT/IB2012/053836 (being published as WO2013/014644) In be described, entire content is incorporated herein by reference.

In certain exemplary embodiments, metal complex is-two alcohol complex of copper.In some embodiments, copper-two Alcohol complex (or copper glycol compound) is the anionic species comprising copper, and shape is complexed by one or more glycol at a high ph in copper At soluble copper complex, generally there is charge 2-.

Glycol includes that at least two hydroxyls to form glycol compound can be reacted with copper material.Increased using alkali compounds PH will form copper 2- complex compound.Charge 2- can be by any suitable cation balance.

In one embodiment, glycol is dihydric alcohol, trihydroxylic alcohol or polyalcohol.In one embodiment, at least two hydroxyl Base is the 1,2- relationship (i.e. adjacent) or 1,3- relationship for being capable of forming-two alcohol complex of metal relative to each other.Suitable glycol Example include but is not limited to ethylene glycol, propylene glycol and glycerol.

In one embodiment, glycol be dihydric alcohol, trihydroxylic alcohol or polyalcohol, or mixtures thereof.In one embodiment In, dihydric alcohol, trihydroxylic alcohol or polyalcohol are C₂-C₂₀Alcohol.In one embodiment, C₂-C₂₀Alcohol is C₂-C₆Dihydric alcohol, trihydroxylic alcohol, Or polyalcohol, polymeric alcohol, or mixtures thereof.

In one embodiment, polymeric alcohol is one or more C₂-C₆The polyethers of dihydric alcohol, trihydroxylic alcohol or polyalcohol polymerize Object.In one embodiment, glycol C₂-C₆Dihydric alcohol, trihydroxylic alcohol or polyalcohol or the polyethers of one or more of them are poly- Close object.

In one embodiment, C₂-C₆Dihydric alcohol, trihydroxylic alcohol or polyalcohol are that low-grade alkylidene or lower alkenylene are sweet Alcohol.In one embodiment, C₂-C₆Dihydric alcohol, trihydroxylic alcohol or polyalcohol are low-grade alkylidene glycol.In one embodiment, C₂-C₆Dihydric alcohol, trihydroxylic alcohol or polyalcohol are low-grade alkylidene glycol or triol.In one embodiment, glycol be selected from by with The group of lower composition: ethylene glycol, propylene glycol, glycerol, or mixtures thereof.In one embodiment, glycol is selected from and is made up of Group: ethylene glycol, glycerol, or mixtures thereof.

In one embodiment, glycol is vicinal diamines.In another embodiment, glycol is polyol.One In a embodiment, glycol is sugar or polyalcohol.

Many glycol are commercially available.

In one embodiment, glycol is selected from the group being made up of: ethylene glycol, propylene glycol, glycerol and its mixing Object.In another embodiment, glycol be ethylene glycol, glycerol, or mixtures thereof.In one embodiment, glycol is ethylene glycol. In another embodiment, glycol is glycerol.

In one embodiment ,-two alcohol complex of metal is formula (I) compound:

Wherein the complex compound generally has 2 negative electrical charges；Wherein R¹And R²It is each independently selected from and is made up of Group: hydrogen, hydroxymethyl, alkyl, alkoxy, substituted carboxyl etc..

In one embodiment, R¹And R²Respectively hydrogen, the compound are copper (II) ethylene glycol complex compound (with two second The copper (II) of glycol ligand connection).

In another embodiment, R¹And R²Respectively methylol, the compound are copper (II) glyceride.

It will be understood by those skilled in the art that when (for example) there is highly basic, formula (I) compound can be had when in the solution Charge (charge is not shown).Charge can be by the way that with necessary chemical ratio, there are any suitable counter ion balances.For example, working as formula (I) when compound has charge -2, anionic charge can be put down by the way that there are a bivalent cations or two univalent cations Weighing apparatus.In one embodiment, counter ion is sodium cation.

Field of coordinative chemistry it should be understood to the one skilled in the art that transition metal can form coordination network in the presence of suitable ligand Close object.For example, copper is capable of forming octahedral coordination complex compound, observed such as in example as described herein is typical dark blue Color.

The example of octahedra copper glycol co-ordination complex is described below.Two alcohol complex of copper is in copper atom and two There are four keys for tool between the oxygen atom of glycol ligand, therefore two other ligands may participate in form the octahedral complex. Suitable other ligand includes (for example) water (as shown below), ammonia (ammonate), amine, alcohol, organic acid, bidentate ligand (example Such as ethylenediamine) or other suitable molecules.The copper complex is generally had 2 negative electrical charges and (is not shown in flowering structure Show), thus in high pH medium have dissolubility and/or with alkali metal forming salt.

Without wishing to be bound by theory, inventor believes that the copper diol compound prepared in following example 1 includes Na₂CuC₆H₁₂O₆.2H₂O。

Those skilled in the art will be appreciated that in addition the complex compound of example 2 is also referred to copper bis ethane -1,2- glycol and closes two hydrations Copper (II) disodium salt.Similarly, if using glycerol as glycol as in other examples, the complex compound can Referred to as 3- hydroxyl propyl- 1,2- glycol close, two hydrations copper (II), disodium salt.

Although term glycol compound can be used in this document to describe this compound, but it is clear that this complex compound is not It is the metal salt of glycolic.In-two alcohol complex of metal, each in one or more glycol includes two or more A hydroxyl, oxygen atom and metal complex.One or more glycol are free of carboxylic acid.

It will be understood by those skilled in the art that different metallicses can accommodate the ligand of different number.The oxygen of metallics The quantity of the open ended ligand of the substance may be will affect by changing state.

The property of the oxidation state and ligand (including glycol ligand) of metallics determines total electricity of-two alcohol complex of metal Lotus.Charge can be as with any suitable cation or (if applicable) anion balance existing for necessary chemical ratio.Sun The example of ion includes metal cation, such as alkali or alkaline earth metal cation, for example, lithium, sodium, potassium, magnesium and calcium sun from Son.The example of anion includes inorganic anion, for example, halide anion (such as fluorine, chlorine, bromine and iodine anion), sulfate radical, Phosphate radical, hydroxyl, nitrate anion, carbonate and heavy carbonic root anion and organic anion, such as alkoxy, acetate And carboxylate radical.Those skilled in the art should be familiar with other cations and anion.

- two alcohol complex of metal includes at least one glycol.In one embodiment ,-two alcohol complex of metal includes two A glycol ligand.In another embodiment, glycol compound includes three glycol ligands.

- two alcohol complex of metal can further include one or more non-glycol ligands.In one embodiment, metal- Two alcohol complexs include one or more water ligands.In another embodiment ,-two alcohol complex of metal includes one or more Alcohol ligand.In another embodiment ,-two alcohol complex of metal includes one or more ammonia ligands or amine ligand.In a reality It applies in example ,-two alcohol complex of metal includes one or more ligands selected from water, alcohol, ammonia, amine and its mixture.

Sometimes preferably with the mixture of ligand.In one embodiment, this ligand may include with ammonia, amine and/or The mixed glycol of water.In one embodiment, this ligand may include the glycol mixed with ammonia and/or amine.In another implementation In example, this ligand may include the glycol mixed with water.The example of suitable amine includes but is not limited to monoethanolamine, diethanol Amine, triethanolamine, ethylenediamine etc..

In some embodiments, the stoichiometric ratio of glycol and metal (such as copper) is about 1:1 to about 3:1, about 1:1 to 2: 1 or about 2:1.

In various embodiments ,-two alcohol complex of metal reacts shape by glycol under alkaline condition and metallics At wherein the glycol is one of ethylene glycol, propylene glycol or glycerol or a variety of.In another embodiment, use is other Glycol.

In certain embodiments, alkaline solution and/or precursor solution include the copper glyceride in water-based liquid medium, Described in the pH of composition be at least about 11, such as 11.5,12,12.5,13,13.5 or 14, useful range can be selected from those Range in value between any two.

As being referred to herein, composition, solution, dispersion, term " aqueous " refers to used in colloid or other liquid The composition, solution, dispersion, colloid or other liquid are by the composition, solution, dispersion, colloid or liquid Poidometer includes at least 10% water, the preferably water of at least 15,20,25 or 30% by weight.

Therefore the alkaline aqueous solution comprising subparticle and/or precursor aqueous solution and/or water-based composition may include by group Close object poidometer about 10 to 99.5% amount water, such as based on the weight of composition about 10 to 99.5,15 to 99.5,20 to 99.5,25 to 99.5,30 to 99.5,35 to 99.5,40 to 99.5,45 to 99.5,50 to 99.5,60 to 99.5,70 to 99.5, 80 to 99.5 or 90 to 99.5%.

Alkaline solution and/or precursor solution and/or water-based composition comprising subparticle can further include it is a kind of or A variety of organic solvents.One or more organic solvents can be alcohol, ketone, lactams, glycol ethers or wherein any two kinds Or more combination.In one embodiment, the alcohol is C₁-C₆Alcohol.In one embodiment, the alcohol is selected from methanol, second Alcohol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol and its mixture.In one embodiment, the alcohol Selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol and its mixture.In one embodiment, the alcohol is selected from the group being made up of Group: methanol, ethyl alcohol and its mixture.In one embodiment, the alcohol is methanol.In another embodiment, the alcohol is Ethyl alcohol.

In various embodiments, comprising by its subparticle formed alkaline aqueous solution and/or precursor aqueous solution and/or Or mixtures thereof aqueous and one or more simple alcohols of water-based composition packet (such as C1-6 alcohol).

The alkaline solution or precursor solution can further include the mixture of glycol or glycol (such as in soluble metal network When conjunction object is-two alcohol complex of metal).

- two alcohol complex of metal can form-two alcohol complex of metal by the preparation of reacting of metal salt and glycol.One In a embodiment, metallics and glycol are reacted in the presence of alkali (such as sodium hydroxide or potassium hydroxide), form network Close object.Those skilled in the art should be familiar with preparing other methods of-two alcohol complex of metal.

In various embodiments, the method can generate free diol, and the glycol can be recycled.

In various embodiments, the method can generate ammonium carbonate, and the ammonium carbonate can be recycled.

On the other hand, the present invention relates to the combinations prepared by the method for the present invention comprising metal salt subparticle Object.

On the other hand, the present invention relates to a kind of method for handling matrix, the method includes to pass through to matrix application Composition prepared according to the methods of the invention comprising metal salt subparticle.

Composition comprising subparticle can be water-based composition as described herein comprising subparticle.Favorably Ground, the water-based composition can be colloidal dispersion form, be suitble to handle lignocellulosic matrix, such as timber.

On the other hand, the present invention relates to the matrixes handled according to the method for the present invention.

Described matrix can be organic matrix.In one embodiment, the organic matrix is lignocellulosic.At one In embodiment, the lignocellulosic matrix is timber or wood composites.In one embodiment, the organic matrix is wood Material.

In one embodiment, the timber sufficiently dry, to allow to be impregnated by the composition.In one embodiment In, described matrix is the timber at or below fibre saturated point.

In certain embodiments, composition of the invention can provide extensive range when providing biocide for matrix, And alleviate the health problem using volatile ammonia or the cost using amine.

Composition of the invention can be used to assign various characteristics for matrix, including biocidal protection or pigmentation.This hair The those of ordinary skill in the bright field being related to, which unquestionably should be appreciated that, can be applied to various compositions of the invention.

By way of example, the processing infected in the infection of harmful organism organism or in advance prevents when being desired, The composition with remove the evil characteristic (such as fungicidal properties, bactericidal characteristic, insecticidal properties) or preservative characteristic can be used (Biocidal composition).

The composition may include for making water-proofing treatment to matrix or providing the compound of flame-retarding characteristic.Handle compound The combination of (such as biocide and fire retardant) will obviously provide beneficial characteristics for matrix.The composition may include inorganic pigment Dispersion is to change the color of matrix.

Although being not intended to be fettered, biocide can include: copper, zinc, cobalt, boron, quaternary ammonium compound, organic iodate Close object, triazole, boron compound, insecticide (such as synthetic pyrethroid etc.) or these mixture.

Fire retardant may include phosphorus-containing compound, guanidine compound, melamine compound, boron compound or these mixing Object.In some cases, the composition include addition emulsifier or surfactant when can be used biocide and/or Fire retardant prepares lotion in solvent combination.

As used herein, " matrix " should refer to any material that can need to deliver composition of the invention；For example, Processing intent is or raw by harmful organism to protect matrix from harmful organism organism on matrix or base intracorporal growth Object removes on matrix or in matrix, perhaps prevent harmful organism organism on matrix or base tumor growth or alleviate Harmful organism organism is on matrix or base tumor growth.This matrix can be lignocellulosic, such as tree living, wooden Product, timber or log.The present invention can be applied over the matrix or essentially dry matrix of the moisture containing certain level, place In or lower than fibre saturated point.The present invention can be applied over inorganic matrix, such as concrete or metal.

Although specification, which specifically focuses on, delivers the composition to timber, plant, leather, painting layer etc., it should be understood that The method can be applied over other matrixes.

At least in the case where lignocellulosic matrix, those of " essentially dry " includes drying by conventional method Timber.Weight ratio of moisture of this timber containing about 1 to about 30 percentage as dry weight of wood, although some In the case of moisture content can be higher.Essentially dry lignocellulosic matrix includes timber, and it is true to have passed through kilning, RF The processing such as sky is dry may be grated as final products or near-final product, and may include that (for example) timber is multiple Condensation material.

" harmful organism " or " harmful organism organism " as mentioned in this article may include can infect organic matrix (such as wood Material) any organism.Although the present invention can especially be applied over fungi, harmful organism organism may also include insect etc.. Fungi and harmful organism will be apparent to those skilled in the art.

As used herein, term " processing (treatment) " should take it most wide in the case where handling matrix Meaning in general range.It should not be construed as showing that matrix is treated as harmful organism organism and is completely removed, although one This in a little embodiments is preferred.The growth of harmful organism organism prevents (such as preventative process) and improvement also by term " processing (treatment) " includes.The relational language as " processing (treating) " etc. should understand in an identical manner.

Subparticle composition can be used by any known mode of composition and material be applied to matrix surface or It is applied to intrinsic silicon.By way of example, the composition by dipping, spray, spraying or brushes application.

Although inventor is not considered as that active pressure must be applied by delivering composition according to the present invention, may be present actively Pressure system (positive pressure or vacuum) can be used to help the case where delivering.It can refer to WO2004/ by way of example in this regard Delivery system described in 054765, is incorporated herein by reference in their entirety.

Although the operation temperature for applying the composition is suitble to (or biocidal can be helped according to subparticle, biocide Agent) (if present) and the composition other components property (such as its solubility etc.) and change, but institute Stating composition can at ambient temperature or about apply at ambient temperature.It can be used up to according to the component of the composition 100 DEG C of temperature.But higher temperature will increase energy consumption.

As discussed herein above, method of the invention can be applied to essentially dry (be saturated at or below fiber Point) matrix.In one embodiment, the composition is applied to the matrix at or below fibre saturated point.

It the content of subparticle can select in amount to used composition and/or composition, to provide expectation Horizontal processing.

In some embodiments, composition of the invention is used to that organic matrix is impregnated or inculcated with metal salt.

In many countries, for timber, there are various processing standards (such as NZ3640), provide preservative and penetrate into timber In and for each danger classes retain given level preservative requirement.Risk class or danger classes are higher, need Retention level it is bigger.For ACQ- type preservative, the reservation of copper is for H3.2, H4 and H5 timber typically respectively about 0.22% M/m, 0.7%m/m and 0.9%m/m.Advantageously, in some embodiments, composition of the invention is used to provide with similar The timber of the reservation of biocide.

In other embodiments, composition of the invention is applied to organic matrix surface as preventative process.

As discussed herein above, the method is optionally including pH adjustment step, to apply by the composition The pH of the composition comprising metal salt subparticle is increased or decreased before to organic matrix.

Composition of the invention can easily be applied to plant living by method in extensive range, such as by impregnating, Spraying is easily applied to plant living by soil application.

Inventors have found that method of the invention can be used to prepare aqueous subparticle Biocidal composition, for heavy Drop and/or cohesion are stable, and it is readily dispersed in water.Current biocide technology is set without using expensive Standby, a large amount of energy cannot provide this simple finely ground particle substance in the case where using expensive solvent.Side of the invention Simple processing technique can be used to carry out for method, and without excessive Capital expenditure, also not need what wet milling techniques were usually directed to High energy.The method can also reduce the demand of the solvent for high-content, surfactant etc., and otherwise it will increase into This is without will increase biological property.

Example

Following non-limiting example is provided to illustrate the present invention, but is in no way intended to limit its range.

Example 1

Into a reaction vessel, addition is equivalent to 1.1g (0.005mol) basic copper carbonate of 0.01mol copper.Thereto Addition 1.9g (0.02mol) glycerol adds 20ml water, obtains the opaque suspension of light green color.It is slowly added 0.4g under agitation (0.01mol) sodium hydroxide, until all basic copper carbonates all be dissolved, obtain a dark blue solution.Copper material is as copper Glyceride (i.e. copper-glycerol complex compound) exists.

0.3g polyacrylic acid dipersant in water is added thereto.The dispersing agent is Orotan 731DP.Mixture is stirred It is dynamic, generate a clear solution.

Arbon dioxide solution is added into clear solution under vigorous agitation.As pH is reduced, insoluble basic carbonate Copper is precipitated from solution, obtains the transparent light green solution of a subparticle dispersion.The dispersion is at least one moon Interior holding is stablized, and does not observe sedimentation or cohesion.

In order to which determination has formed subparticle dispersion, a certain amount is placed in clear, colorless container.Pass through container When dispersion is observed, visually see it being fully transparent (as shown in Figure 1).But when the arrow beam of light of LED based light source irradiates When by the fluid, the region that light passes through is in muddy (as shown in Figure 2).This observation result of Tyndall effect determines Generate colloidal state or subparticle dispersion.

Use the Mastersizer 2000Ver.5.60 from England Malvern Malvern Instruments Ltd The particle size distribution of composition sample is tested.Particle size distribution is shown in Figure 3.Obviously, the particle of preparation exists In the range of 100nm to 400nm.It is shown as the artefact that the distribution of particles from 2 to 30um is considered as test method.

Example 2

The colloidal dispersion that basic copper carbonate is prepared according to the step identical as described in example 1, in addition to glycerol is counted by chemistry The ethylene glycol substitution of equivalent is calculated (to form copper-ethylene glycol complex compound or copper ethylene glycol compound, rather than copper glyceride or copper- Glycerol complex compound).

Example 3

Copper glyceride solution is prepared according to the step of described in example 1.0.3g polyacrylate in water is added thereto Dispersing agent.The dispersing agent is Orotan 731DP.The mixture is stirred, a clear solution is generated.

Carbon dioxide gas is bubbled by the clear solution, until pH is brought down below 10.This generates basic copper carbonate Transparent subparticle dispersion.With equally prove that there are colloidal dispersions using light beam (observe Tyndall effect) in example 1 Body.

Example 4

Copper glyceride solution is prepared according to the step of described in example 1.The polyacrylic acid of 0.3g in water is added thereto Dipersant.The dispersing agent is Orotan 731DP.The mixture is stirred, a clear solution is generated.

Carbon dioxide gas is bubbled by the clear solution, until pH is down to 9.This generates the saturating of basic copper carbonate Bright subparticle dispersion.With in example 1 equally using light beam prove there are colloidal dispersions.

Example 5

Copper glyceride solution is prepared according to the step of described in example 1.The polyacrylic acid of 0.1g in water is added thereto Dipersant.The dispersing agent is Orotan 731DP.Mixture is stirred, a transparent fluid is generated.

Carbon dioxide gas is bubbled by the clear solution, until pH is down to 10.This generates basic copper carbonates Transparent subparticle dispersion.With in example 1 equally using light beam prove there are colloidal dispersions.

Example 6

Into a reaction vessel, addition is equivalent to 1.1g (0.005mol) basic copper carbonate of 0.01mol copper.Thereto Addition 1.9g (0.02mol) glycerol adds 2ml water, obtains the opaque suspension of light green color.0.3g Orotan is added thereto 731DP.Be slowly added 0.4g (0.01mol) sodium hydroxide under agitation, until all basic copper carbonates all be dissolved, generate one A dark blue solution.Copper material exists as copper glyceride.

The water that 140ml is saturated at 10 DEG C by carbon dioxide is added into the solution.This generates basic copper carbonate colloidal state Dispersion.PH is 10.

Example 7

1.1g (0.005mol) the basic copper carbonate preparation of 0.01mol copper is equivalent to by adding into a reaction vessel Carbonic acid cuoxam.0.4g (0.005mol) ammonium carbonate is added together with 20ml water.0.3g Orotan 731DP is stirred to this In solution.Be slowly added ammonia solution (S.G.0.880) under agitation, until basic copper carbonate is completely dissolved, obtain one it is non- Often dark blue solution.

The water being saturated at 10 DEG C by carbon dioxide is added under vigorous agitation, until pH is 7.This generates transparent light blue Basic copper carbonate subparticle dispersion.

The dissolution of copper carbonate can be improved including ammonium carbonate, but is not necessary.

The scanning electron micrograph of dispersion granule is shown in FIG. 4.The 2um scale in the lower right corner is divided into 10 200nm increment.As can be seen that particle size is about 200nm.

Example 8

The basic copper carbonate dispersion samples prepared in example 5 are heated to 80 DEG C, carry out 10 minutes periods.Dispersion It deepens as dark brown color.This is copper oxide disperses body.

Example 9

The sample of the basic copper carbonate dispersion prepared in example 7 is tested in corrosion research.By two mild steel Metal testing plate is placed in the dispersion of certain volume.There is no signs of corrosion in steel test piece after 7 days.

In general, by corroding in the displacement to test piece of the copper of solution, this passes through the deposition or on the metal surface of copper The various oxides of copper and/or iron are formed to recognize.Steel test piece keeps bright and bright, shows not replace.

The further research for comparing general AC Q and composition of the invention is carried out.It is prepared for copper concentration phase Same solution adds steel test piece, and visual monitoring.In 4 days, the test piece for being exposed to ACQ shows corrosion and black deposit Formation, appearance changes completely.The test piece for being exposed to composition of the invention keeps bright and bright after 5 weeks.

Example 10

Prepare carbonic acid cuoxam according to the step of described in example 7, in addition to a kind of 0.15g Corolan OT (naphthalene sulphur Sour formaldehyde condensation products) 0.15g Orotan 731DP is added together, rather than add 0.3g Orotan 731DP.

Sample is purged with carbon dioxide gas under vigorous agitation.This generates transparent basic copper carbonate subparticles point Granular media.

Example 11

0.1g surfactant-dispersed agent neopelex is added before adding carbon dioxide.

Then sample is purged with carbon dioxide gas under vigorous agitation.This generates transparent basic copper carbonate sub-micros Grain dispersion.

Example 12

Prepare zinc carbonate colloidal dispersion.0.01mol zinc oxide is added into 20ml water.0.01mol carbon is added thereto The ammonia (0.85g) plus 0.3g Orotan 731DP of sour hydrogen ammonium (0.79g) plus 30% aqueous solution form of 0.05mol, generate one Transparent colourless solution.

The water being saturated by carbon dioxide is added under vigorous agitation, until pH is about 7.It is complete for naked eyes this generates one The colourless fluids of all-transparent.When being irradiated with arrow beam of light, zinc carbonate colloidal dispersion can be seen in light beam, in above example That observes is similar.

Example 13

The specification of association is protected to prepare ACQ (ammoniacal copper quaternary) timber preservative sample according to american wood.The sample is to include The type of copper carbonate, ammonia and Carboquat.It includes the 1.1g basic copper carbonate for being equivalent to 0.83g copper oxide (0.01mol), Add 0.41g didecyldimethylammonium ammonium carbonate as Carboquat.Addition 0.005mol ammonium hydrogen carbonate (0.4g) adds thereto The ammonia of 30% aqueous solution form of 2.28g.The sample is a navy blue clear aqueous fluid.

Take the aliquot for being equivalent to 1.1g basic copper carbonate.A kind of (the epoxy second of 0.4g Atlox 4894 is added thereto Alkane/epoxy propane copolymer non-ionic dispersing agent).As non-ionic dispersing agent, Atlox 4894 and cationic surfactant Carboquat is compatible.It avoids using anionic surfactant or dispersing agent (such as neopelex), this is because This can cause to precipitate by reacting with cationic surfactant.

The water being saturated by carbon dioxide is added under vigorous agitation.This generates a copper carbonate powder blue dispersion, Didecyldimethylammonium ammonium carbonate retains in the solution.

Example 14

It prepares ACQ sample as follows: exposed copper wire being placed in ammonia/ammonium bicarbonate aqueous solution first, is used air as Oxidant, until copper is completely dissolved.Didecyldimethylammonium ammonium carbonate is added into the aliquot of solution, is obtained such as example 13 Described in ACQ solution.

0.4g Atlox 4894 is added thereto.Then the water being saturated by carbon dioxide is added under vigorous agitation.This is produced The optically transparent copper carbonate dispersion of a powder blue is given birth to.

Example 15

Basic copper carbonate colloidal dispersion is prepared according to the step of described in above example 7, in addition to Orotan is replaced by 0.3g polyvinylpyrrolidone (K15).This generates a kind of flocculating compositions, and stable sub-micro is provided when being diluted with water Grain dispersion.

Example 16

Basic copper carbonate colloidal dispersion is prepared according to the step of described in water example 7, in addition to Orotan is replaced by 0.3g polyvinylpyrrolidone (K15).0.1g neopelex in water is added into resulting composition.This generates steady Fixed subparticle dispersion.The dispersion is stable when further being diluted with water.

Example 17

1.1g (0.005mol) the basic copper carbonate preparation of 0.01mol copper is equivalent to by adding into a reaction vessel Carbonic acid cuoxam.0.4g (0.005mol) ammonium carbonate is added together with 20ml water.0.3g Orotan 731DP is stirred to this In solution.Be slowly added ammonia solution (S.G.0.880) under agitation, until basic copper carbonate is completely dissolved, obtain one it is non- Often dark blue solution.Then 0.6g borax (sodium tetraborate) pentahydrate is added.

The water that addition is saturated at 10 DEG C by carbon dioxide under vigorous agitation, until pH is down to 9.Pass through the vision fluid Remain transparent blue solution (being transparent blue fluid for naked eye).The fluid is stable mantoquita subparticle colloidal state Dispersion.

It is believed by the inventors that the fluid may include alkali formula copper borate subparticle.

Example 18

Basic copper carbonate colloidal dispersion is prepared according to the step of described in above example 7, in addition to 0.3g Orotan is substituted For 0.4g Atlox 4894.

The alkali of stoichiometric amount is carefully added into blue solution, removes carbonate anion for the carbon of generation will pass through Sour copper is converted into Kocide SD.This is proved by therefrom blue to color change azury.

Then the sample is heated to 80 DEG C, carried out 4 minutes, thus Kocide SD is converted into the copper oxide of black.

Example 19

It is prepared by the step of carbonic acid cuoxam is according to described in example 7.

The water being saturated at 10 DEG C by carbon dioxide is added under agitation, until pH is 8.It is transparent light blue this generates one The basic copper carbonate subparticle dispersion of color.

Example 20

0.2g sodium tetraborate tetrahydrate is added in the sample of the basic copper carbonate dispersion prepared into above example 19. After stirring and ensuring to be completely dissolved, pH is measured as 9.Precipitating is not observed；Dispersion keeps transparent.

Example 21

0.2g sodium tetraborate pentahydrate is added in the sample of the dispersion prepared into above example 13.Agitation and it is true After guarantor is completely dissolved, pH is measured as 9.Precipitating is not observed.

Example 22

Boron is prepared by 1.5g (0.005mol) copper borate that addition is equivalent to 0.005mol copper into a reaction vessel Sour cuoxam.0.3g Orotan 731DP is stirred in the solution.It is slowly added ammonia solution under agitation (S.G.0.880), until alkali formula copper borate is completely dissolved, a very dark blue solution is obtained.

The water being saturated at 10 DEG C by carbon dioxide is added under agitation, until pH is 8.It is transparent light blue this generates one The dispersion of color is considered as alkali formula copper borate subparticle.

Example 23

The specification of association is protected to prepare ACQ (ammoniacal copper quaternary) timber preservative sample according to american wood.The sample is to include The type of copper carbonate, ammonia and Carboquat.This adds comprising being equivalent to the 1.1g basic copper carbonate of 0.83g copper oxide (0.01mol) 0.41g didecyldimethylammonium ammonium carbonate is as Carboquat.Addition 0.005mol ammonium hydrogen carbonate (0.4g) plus 2.28g thereto The ammonia of 30% aqueous solution form.The sample is navy blue clear aqueous fluid.

Take the aliquot for being equivalent to 1.1g basic copper carbonate.

The water being saturated by carbon dioxide is added under agitation.This generates the dispersions of the transparent copper carbonate of a powder blue Body, didecyldimethylammonium ammonium carbonate retain in the solution.

Compared with the step of described in the example 13, it is not added with Altox4894.

Without wishing to be bound by theory, it is believed by the inventors that the subparticle dispersion of insoluble metallic salt is carbonated ammonium It stabilizes without assembling and/or settling, the ammonium carbonate is formed when adding carbon dioxide in the ammino-complex into solution. Two molecule ammonium carbonates are generated when adding carbon dioxide and decomposing each soluble metal complex compound.

Example 24

Some plain bar test pieces are added in the sample of the dispersion prepared into example 19 to act on evaluation of corrosion.One week it The appearance of steel test piece or liquid composition does not change afterwards.

Above example proves that the subparticle dispersion of metal carbonate and/or borate can pass through the simple of low cost Technology preparation is without using expensive device and equipment to be ground, and corresponding metal hydroxides and metal oxidation Object can also be prepared by this method.

Industrial applicibility

The composition comprising subparticle generated by means of the present invention can be used for various applications, this is for this field It will be apparent for technical staff.For example, the composition comprising biocidal metal salt subparticle can be used to handle base Body is to fight biodegrade or harmful organism.Particularly, the composition can be used to handle lignocellulosic matrix (such as wood Material), plant (including cereal crops), other biodegradable matrixes (including leather), inorganic matrix (such as concrete), with And abiotic matrix (such as painting layer).The composition can be used for example for preventing harmful organism organism (such as harmful Fungi) growth purpose, or for providing specific characteristic for matrix.The subparticle also may include metal compound Object can be used as pigment, also act as or be converted into catalyst.

Following paragraphs is related to various aspects of the invention and each embodiment:

1. a kind of method for preparing the composition comprising metal salt subparticle, the method includes:

2. method described in paragraph 1, wherein the water-based composition is colloidal dispersion；Or the water-based composition is Flocculated composition, the method is further included goes to flocculate by the composition, to provide colloidal dispersion.

3. method described in paragraph 1 or 2, wherein solution to be mixed to the pH that can reduce solution with carbon dioxide source, so as to gold Belong to carbonate subparticle precipitating.

4. method described in either segment in aforementioned paragraphs, it includes by solution, carbon dioxide source and one or more weak The source mixing of acid, to reduce the pH of solution, so as to metal salt subparticle precipitating.

5. method described in paragraph 4, wherein the weak acid is the weak acid of the pKa at least about 6.

6. method described in paragraph 4 or 5, wherein the weak acid is essentially insoluble for that can be formed with metal in the water of pH7 The weak acid of the salt of property.

7. method described in either segment in paragraph 4-6, wherein the weak acid is boric acid or phenol.

8. method described in paragraph 7, wherein the weak acid source is boric acid or borate.

9. method described in either segment in aforementioned paragraphs, wherein the water-based composition includes metal carbonate sub-micro Grain, and the method is further included the water-based composition alkali process comprising metal carbonate subparticle, to provide Water-based composition comprising metal hydroxides subparticle；And optionally by the water comprising metal hydroxides subparticle Property composition heating, with provide include metal oxide subparticle water-based composition.

10. method described in either segment in aforementioned paragraphs, wherein the water-based composition includes metal carbonate sub-micro Grain or metal hydroxides, the method, which further includes, to be heated comprising the water-based composition of metal carbonate subparticle, To provide the water-based composition for including metal oxide subparticle.

11. method described in either segment in aforementioned paragraphs, wherein the carbon dioxide source is carbon dioxide gas, includes two The solution of carbonoxide, potential carbon dioxide source or the wherein arbitrarily combination of two or more.

12. method described in either segment in aforementioned paragraphs, wherein the carbon dioxide source is carbon dioxide gas or packet Carbonated solution.

13. method described in either segment in aforementioned paragraphs is less than wherein the metal salt has in water at 20 DEG C The solubility of 0.1g/L.

14. method described in either segment in aforementioned paragraphs, wherein it is about 4.5 to about 9 that the pH of the solution, which is reduced to pH,.

15. method described in either segment in aforementioned paragraphs, wherein offer alkaline aqueous solution includes:

Mix one or more dispersing agents.

16. method described in either segment in aforementioned paragraphs, wherein providing alkaline solution or alkaline precursor solution included in packet Source metal can be formed into soluble complexes with metal under alkaline condition with one or more in aqueous alkalescence medium containing alkali Ligand reaction.

17. method described in paragraph 16, wherein the alkali is alkali metal hydroxide (such as sodium hydroxide or hydroxide Potassium), ammonia or amine.

18. method described in paragraph 16 or 17, wherein the source metal is metallic compound or metal element.

19. method described in either segment in aforementioned paragraphs, wherein the pH of the alkaline solution and/or alkaline precursor solution is At least 9.

20. method described in either segment in aforementioned paragraphs, wherein one or more of ligands are selected from and to be made up of Group: ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.

21. method described in either segment in aforementioned paragraphs, wherein one or more of ligands are selected from and to be made up of Group: glycerol, ethylene glycol and ammonia.

22. method described in either segment in aforementioned paragraphs, wherein the metal is first, second or third transition series Metal.

23. method described in either segment in aforementioned paragraphs, wherein the metal is copper or zinc.

24. method described in either segment in aforementioned paragraphs, wherein alkaline aqueous solution and/or alkaline precursor aqueous solution and/or Water-based composition includes one or more organic solvents.

25. method described in either segment in aforementioned paragraphs, wherein before alkaline aqueous solution and/or alkalinity comprising subparticle Body aqueous solution and/or water-based composition further include one or more surfactants.

26. method described in either segment in aforementioned paragraphs, further include by one or more surfactants with comprising The alkaline solution of subparticle and/or alkaline precursor solution and/or water-based composition mixing.

27. method described in either segment in aforementioned paragraphs, further include by one or more other dispersing agents with Alkaline solution comprising subparticle and/or water-based composition mixing.

28. method described in either segment in aforementioned paragraphs, wherein the dispersing agent are as follows: anionic dispersing agents, such as poly- carboxylic Hydrochlorate (such as polyacrylate), naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, condensate of melamine sulfonate and formaldehyde, Alkyl-aryl-group ether phosphate or alkyl ether phosphate；Cation dispersing agent；Non-ionic dispersing agent, such as polyethers, including mixing Polyethers；Amphoteric ion dispersing agent, such as amphoteric ion polymer；Or the wherein arbitrarily combination of two or more.

29. method described in either segment in paragraph 25-28, wherein the surfactant is anionic surfactant, Such as dodecyl benzene sulfonate, lauryl sulfate or lauryl sulfate；Cationic surfactant, such as benzene are pricked Oronain or cetyl trimethylammonium bromide；Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol polyoxy Vinethene；Zwitterionic surfactant；Or the wherein arbitrarily combination of two or more.

30. method described in either segment in aforementioned paragraphs is further included through mixed acid or alkali and is adjusted comprising Asia The pH of the alkaline solution of microparticle and/or alkaline precursor solution and/or water-based composition.

31. method described in either segment in aforementioned paragraphs, wherein the water-based composition comprising subparticle is to mark To the colloidal dispersion of cohesion and/or settlement stability within 1,2,3,4,5,6 or 7 day period under the conditions of standard.

32. method described in either segment in aforementioned paragraphs, wherein the composition comprising subparticle further includes one kind Or a variety of biocides.

33. method described in paragraph 32, wherein the biocide be fungicide, it is insecticide, mildewcide, bactericidal Agent or algicide.

34. method described in either segment in aforementioned paragraphs, further include by one or more biocides with comprising The composition of subparticle mixes.

35. method described in either segment in paragraph 32-34, wherein one or more biocides be solution, lotion, Microencapsulation or subparticle form.

36. method described in either segment in aforementioned paragraphs, wherein the composition comprising subparticle includes one or more The subparticle of biocide.

37. a kind of combination comprising metal salt subparticle by according to the method preparation of either segment in aforementioned paragraphs Object.

38. a kind of method for handling matrix, the method includes to apply to matrix by according to any one of aforementioned paragraphs Method preparation the composition comprising metal salt subparticle.

39. a kind of matrix by being handled according to the method for paragraph 38.

Although the present invention is described by way of example and with reference to specific embodiment, it should be appreciated that can It modifies and/or changes in the case of without departing from the scope of the present invention.

The complete disclosure of all applications, patent and publication (if any) that above and below is quoted all passes through It is incorporated herein by reference.

Claims

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with the metal under alkaline condition Ligand and optional one or more dispersing agents；And

The solution and carbon dioxide source are mixed, to reduce the pH of the solution, so as to metal salt subparticle precipitating, thus The water-based composition of subparticle comprising the metal salt is provided.

2. according to the method described in claim 1, wherein the method includes:

It provides and wraps metalliferous alkaline aqueous solution, one or more can form soluble complexes with the metal under alkaline condition Ligand and one or more dispersing agents.

3. method according to claim 1 or 2, wherein the water-based composition is colloidal dispersion；Or it is described aqueous Composition is flocculating composition, and the method is further included goes to flocculate by the composition, to provide colloidal dispersion.

4. according to the method in any one of claims 1 to 3, wherein the solution is mixed meeting with the carbon dioxide source The pH of the solution is reduced, so as to metal carbonate subparticle precipitating.

5. method according to claim 1 to 4, wherein the solution is mixed meeting with the carbon dioxide source The pH of the solution is reduced, so as to metal borate subparticle precipitating.

6. method according to any of the preceding claims, wherein the soluble metal complex compound is reducing the alkali It can be decomposed when the pH of property solution.

7. method according to any of the preceding claims, wherein the soluble metal complex compound can be with the dioxy Change the carbon dioxide reaction that carbon source provides.

8. method according to any of the preceding claims, wherein the one or more of the soluble metal complex compound Ligand is discharged from the soluble metal complex compound and/or one or more ligands of the soluble metal complex compound Salt generated by the decomposition of the soluble metal complex compound.

9. method according to any of the preceding claims, wherein one or more of ligands or its salt can reduce or Prevent the aggregation and/or sedimentation of the subparticle.

10. method according to any of the preceding claims, wherein one or more of ligands or its salt are selected from carbon The carbonate and glycol of sour ammonium, amine.

11. method according to any of the preceding claims, wherein the solution further include it is one or more weak The source of acid.

12. method according to any of the preceding claims, it includes by the solution, carbon dioxide source, Yi Jiyi The source of kind or a variety of weak acid mixing, to reduce the pH of the solution, so as to metal salt subparticle precipitating.

13. according to the method for claim 12, wherein the weak acid is the weak acid of the pKa at least about 6.

14. method according to claim 12 or 13, wherein the weak acid is that can be formed with the metal in the water of pH7 The weak acid of the salt of essentially insoluble property.

15. method described in any one of 2-14 according to claim 1, wherein the weak acid is boric acid or phenol.

16. according to the method for claim 15, wherein the source of the weak acid is boric acid or borate.

17. method according to any of the preceding claims, wherein the water-based composition includes the carbon of the metal The subparticle of hydrochlorate, and the method is further included the described aqueous of the carbonate subparticle comprising the metal Composition alkali process, to provide the water-based composition of the hydroxide subparticle comprising the metal；And optionally will The water-based composition of hydroxide subparticle comprising the metal heats, to provide the oxide for including the metal The water-based composition of subparticle.

18. method according to any of the preceding claims, wherein the water-based composition includes the carbon of the metal The subparticle of the hydroxide of hydrochlorate or the metal, and the method is further included the carbonic acid comprising the metal The water-based composition of the subparticle of salt heats, to provide aqueous group of the subparticle of the oxide comprising the metal Close object.

19. method according to any of the preceding claims, wherein the carbon dioxide source is carbon dioxide gas, packet Carbonated solution, potential carbon dioxide source or the wherein arbitrarily combination of two or more.

20. method according to any of the preceding claims, wherein the carbon dioxide source be carbon dioxide gas or Person wraps carbonated solution.

21. method according to any of the preceding claims, wherein the metal salt is at 20 DEG C in water with small In the solubility of 0.1g/L.

22. method according to any of the preceding claims, wherein it is about 4.5 to about that the pH of the solution, which is reduced to pH, 9。

23. method according to any of the preceding claims, wherein the pH of the solution be reduced to pH be about 7.5 to 9.5。

24. method according to any of the preceding claims, wherein it is about 8 to 9 that the pH of the solution, which is reduced to pH,.

25. method according to any of the preceding claims, wherein providing the alkaline aqueous solution and including:

There is provided the metalliferous alkaline precursor aqueous solution of packet and it is one or more can be formed under alkaline condition with the metal it is solvable The ligand of complex compound；And

Optionally mix one or more dispersing agents.

26. method according to any of the preceding claims, wherein providing the alkaline aqueous solution and including:

Mix the one or more dispersing agents.

27. method according to any of the preceding claims, wherein providing the alkaline solution or alkaline precursor solution Include in the aqueous alkalescence medium comprising alkali by the source of the metal with it is one or more under alkaline condition can with it is described The ligand reaction of metal formation soluble complexes.

28. according to the method for claim 27, wherein the alkali is alkali metal hydroxide (such as sodium hydroxide or hydrogen-oxygen Change potassium), ammonia or amine.

29. the method according to claim 27 or 28, wherein the source of the metal is metallic compound or metal element.

30. method according to any of the preceding claims, wherein the alkaline solution and/or alkaline precursor solution PH is at least 9.

31. method according to any of the preceding claims, wherein one or more of ligands are selected from by with the following group At group: ammonia, amine and glycol, such as dihydric alcohol, trihydroxylic alcohol and polyalcohol.

32. method according to any of the preceding claims, wherein one or more of ligands are selected from by with the following group At group: glycerol, ethylene glycol and ammonia.

33. method according to any of the preceding claims, wherein the metal is first, second or third transition Series metal.

34. method according to any of the preceding claims, wherein the metal is copper or zinc.

35. method according to any of the preceding claims, wherein the alkaline aqueous solution and/or alkaline precursor are water-soluble Liquid and/or water-based composition include one or more organic solvents.

36. method according to any of the preceding claims, wherein the alkaline aqueous solution comprising subparticle and/ Or alkaline precursor aqueous solution and/or water-based composition further include one or more surfactants.

37. method according to any of the preceding claims is further included one or more surfactants It is mixed with the alkaline solution comprising subparticle and/or alkaline precursor solution and/or the water-based composition.

38. method according to any of the preceding claims is further included one or more other dispersions Agent is mixed with the alkaline solution comprising subparticle and/or the water-based composition.

39. method according to any of the preceding claims, wherein the dispersing agent are as follows: anionic dispersing agents, such as The polycarboxylate of such as polyacrylate, naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, melamine sulfonate and formaldehyde condensation Object, alkyl-aryl-group ether phosphate or alkyl ether phosphate；Cation dispersing agent；Non-ionic dispersing agent, it is poly- for example including mixing The polyethers or polyvinylpyrrolidone of ether；Amphoteric ion dispersing agent, such as amphoteric ion polymer；Or wherein any two kinds Or more combination.

40. the method according to any one of claim 36-39, wherein the surfactant are as follows: anionic surface is living Property agent, such as dodecyl benzene sulfonate, lauryl sulfate or lauryl sulfate；Cationic surfactant, such as Benzalkonium chloride or cetyl trimethylammonium bromide；Nonionic surfactant, such as nonylphenol polyoxyethylene ether or octyl phenol Polyoxyethylene ether；Zwitterionic surfactant；Or the wherein arbitrarily combination of two or more.

41. method according to any of the preceding claims, further includes and include by mixed acid or alkali adjusting The pH of the alkaline solution of subparticle and/or the alkaline precursor solution and/or the water-based composition.

42. according to the method for claim 41, wherein pH is adjusted by mixing boric acid and/or the borate as borax Section.

43. method according to any of the preceding claims, wherein the water-based composition comprising subparticle It is about 7.5 to 9.5 that pH, which is adjusted to pH by mixed acid or alkali,.

44. method according to any of the preceding claims, wherein the water-based composition comprising subparticle It is about 8 to 9 that pH, which is adjusted to pH by mixed acid or alkali,.

45. method according to any of the preceding claims, wherein the water-based composition comprising subparticle is At the standard conditions to the colloidal dispersion of cohesion and/or settlement stability within 1,2,3,4,5,6 or 7 day period.

46. method according to any of the preceding claims, wherein the composition comprising subparticle is further Include one or more biocides.

47. according to the method for claim 46, wherein the biocide is fungicide, insecticide, mildewcide, kills Bacteriocin or algicide.

48. method according to any of the preceding claims, further include by one or more biocides with Composition mixing comprising subparticle.

49. the method according to any one of claim 46-48, wherein one or more biocides be solution, Lotion, microencapsulation or subparticle form.

50. method according to any of the preceding claims, wherein the composition comprising subparticle is further Subparticle comprising one or more biocides.

51. method according to any of the preceding claims, wherein when using the 12 Corrosion standards method of AWPAE When test, the composition can generate at least low 20% mpy compared with standard ACQ.

52. a kind of group comprising metal salt subparticle prepared by method according to any of the preceding claims Close object.

53. a kind of method for handling matrix, the method includes to apply to described matrix by appointing according in preceding claims The composition comprising metal salt subparticle of the preparation of method described in one.

54. a kind of matrix by being handled according to the method for claim 53.